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The area of what is today Union City was originally inhabited by the Munsee-speaking branch of Lenape Native Americans, who wandered into the vast woodland area encountered by Henry Hudson during the voyages he conducted from 1609 to 1610 for the Dutch, who later claimed the area (which included the future New York City) and named it New Netherland. The portion of that land that included the future Hudson County was purchased from members of the Hackensack tribe of the Lenni-Lenape and became part of Pavonia, New Netherland.

The relationship between the early Dutch settlers and Native Americans was marked by frequent armed conflict over land claims. In 1658 by New Netherland colony Director-General Peter Stuyvesant re-purchased the territory. The boundaries of the purchase are described in the deed preserved in the New York State Archives, as well as the medium of exchange: "80 fathoms of wampum, 20 fathoms of cloth, 12 brass kettles, 6 guns, one double brass kettle, 2 blankets, and one half barrel of strong beer." In 1660, he ordered the building of a fortified village at Bergen to protect the area. It was the first permanent European settlement in New Jersey, located in what is now the Journal Square area of Jersey City near Academy Street. In 1664, the British captured New Netherland from the Dutch, at which point the boundaries of Bergen Township encompassed what is now known as Hudson County. North of this was the unpopulated Bergen Woods, which would later be claimed by settlers, after whom a number of Union City streets today are named, including Sipp Street, Brown Street, Golden Lane, Tournade Street and Kerrigan Avenue, which is named after J. Kerrigan, the owner of Kerrigan Farm, who donated the land for Saint Michael's Monastery.

The area that would one day be Union City, however, remained sparsely populated until the early 19th century. The British granted Bergen a new town charter in 1668. In 1682 they created Bergen County, which was named to honor their Dutch predecessors. That county comprised all of present-day Hudson, Bergen and Passaic counties. Sparsely inhabited during the 17th and 18th centuries, the southeast section of Bergen County had grown by the early 19th century to the point where it was deemed necessary to designate it a separate county. The New Jersey legislature created Hudson County in 1840, and in 1843, it was divided into two townships: Old Bergen Township (which eventually became Jersey City) and North Bergen Township, which was gradually separated into Hudson County's present day municipalities: Hoboken in 1849, Weehawken and Guttenberg in 1859, and West Hoboken and Union Township. West Hoboken was incorporated as a township by an act of the New Jersey Legislature on February 28, 1861, from portions of North Bergen Township. The township was reincorporated on April 6, 1871, and again on March 27, 1874. Portions of the township were ceded to Weehawken in 1879. On June 28, 1884, West Hoboken was reincorporated as a town, based on an ordinance passed nine days earlier. The town was reincorporated on April 24, 1888, based on the results of a referendum passed 12 days earlier. Union Township, or simply Union, was formed through the merger of a number of villages, such as Dalleytown, Buck's Corners and Cox's Corners. The largest of these villages, Union Hill, became the colloquial name for the merged town of Union itself. The northern section of Union Township was later incorporated as West New York in 1898. Union City was incorporated on June 1, 1925, by merging the two towns of West Hoboken and Union Hill. The name of one of the city's schools, Union Hill Middle School, recalls the former town.

In the 18th century, Dutch and English merchants first settled the area. Later, German immigrants immigrated from Manhattan. Irish, Polish, Armenians, Syrians, Eastern European Jews and Italians followed. In 1851, Germans moved across the Hudson River from New York City in search of affordable land and open space. During the Civil War a military installation, Camp Yates, covered an area now bounded by Bergenline and Palisade Avenues from 22nd to 32nd Street. Germans began to settle what would become Union Hill in 1851, and some descendants of the immigrants of this period live in the city today. Although the area's diversity was represented by the more than 19 nationalities that made their home in the Dardanelles (a five-block area of Central Avenue from 23rd Street to 27th Street) from the mid-19th century to the early 20th century, German Americans and Dutch dominated the area. Along with Swiss and Austrian immigrants, they founded the European-style lace making industries for which they were famous. The introduction of Schiffli lace machines in Hudson County made Union City the "embroidery capital of the United States". The trademark of that industry is on the Union City Seal, though foreign competition and austere prevailing fashions led to the decline of embroidery and other industries in the area by the late 1990s. In May 2014 the city dedicated "Embroidery Square" at New York Avenue to commemorate that history.

As immigration to the area progressed throughout the 19th and 20th centuries, Belgians, Armenians, Greeks, Chinese, Jews and Russians found a home in the area, though its domination by Germans by the turn of the 20th century was reflected in the fact that the minutes of town meetings were recorded in German. By this time, the area was witnessing a period of urbanization, as an extensive trolley system was developed by the North Hudson County Railway, spurred by both electrification in 1890 and the arrival of Irish and Italian immigrants, which dominated the city until the late 1960s. Successive waves of immigrants from Eastern Europe, the Near East and Latin America contributed to the embroidery industry in subsequent years. "The Cultural Thread"/"El Hilo", an exhibit highlighting this industry, is on display at Union City's Park Performing Arts Center.

The town was famous for being the home of the rowdy Hudson Burlesque. Theaters in Union City featured vaudeville and burlesque and acts including Fred Astaire and Harry Houdini. It was at a vaudeville theater in Union City that comedian George Burns would meet his longtime partner and wife, Gracie Allen. Union City was also for a time the home to the headquarters of sports publisher Joe Weider.

The first Cubans immigrated to Union City from New York City in the late 1940s, having been attracted to the city in search of work after hearing of its famed embroidery factories. A majority of these Cubans hailed from small towns or cities, particularly Villa Clara Province in central Cuba. After World War II, veterans relocated to Bergen County, causing a short-lived decline in the population. By the 1960s the city was predominantly an old-line Italian enclave. This began to change when large numbers of Cubans emigrated to the city after Fidel Castro took power in 1962. This made Union City for many years the city with the largest Cuban population in the U.S. after Miami, hence its nickname, "Little Havana on the Hudson." Following the Mariel boatlift in 1980, 10,000 Cubans settled in New Jersey, leading to a second wave of Cubans to Union City, which totaled 15,000 by 1994. The city, as well as neighboring towns such as West New York, experienced a profound cultural impact as a result of this, as seen in such aspects of local culture as its cuisine, fashion, music, entertainment and cigar-making.

Amid a redevelopment boom in the early 1960s, The Troy Towers, a 22-story twin tower luxury apartment complex, was completed in 1966 on the edge of the Palisades cliffs on Mountain Road at 19th Street, at the former site of the Abbey Inn, just north of where a motorized vehicle elevator and a staircase called the Lossburg Steps were located. The former was an angled ramp originally built for horse-drawn carriages, which along with the steps, connected to Hackensack Plank Road beneath the cliffs, in the Shades section of Weehawken. According to the Hudson County Multiple Listing service, between 2016 and 2018 the median list price of residential properties on the market in Union City fluctuated between $345,000 and $509,000. The most expensive home on the market in May 2018 was a four-family building on sale for $1.6 million, while the lowest was a studio apartment in Troy Towers for $148,000. A typical residential property was a six-bedroom, three-family house in need of updating, listed at $568,000.

Since its inception in 2000, the Cuban Day Parade of New Jersey became a major annual event in North Hudson, beginning in North Bergen and traveling south to its end in Union City. Union City has historically been a family-oriented city predominantly made up of brownstones, two-family homes and locally owned businesses. Another wave of modestly sized residences began development approximately in 2003, spurred by similar development in neighboring Hoboken, and the city's attempt to attract developers to what had historically been a town unfriendly to them, according to Mayor Brian P. Stack. Through approval of varied construction projects to address the needs of residents of different incomes, improved rent control laws and community input on such issues, this "Hobokenization" resulted in positive comparisons with the redeveloped Hoboken of the mid-to-late 1990s, with new restaurants, bars, and art galleries cited as evidence of renewal. The city recorded $192 million in new construction in 2007, and 600 certificates of occupancy, with 500-700 projected for 2008–2009, compared with previous years, in which 50 certificates was considered a high amount. This development continued for several years, reaching a milestone in 2008 with the completion of Union City's first high-rise condominium tower, The Thread, whose name evokes the city's historical association with the embroidery industry. Other such buildings followed, such as the Altessa, Park City Grand, and Hoboken Heights. In 2015, the AARP ranked Union City #6 on its list of the best small cities to live in.

Union City is a working class community. One of Hudson County's three homeless shelters, Palisades Emergency Residence Corp. (PERC), is located in Union City. The PERC facility, which includes a soup kitchen, food pantry and 40-bed shelter on 37th Street, lost $100,000 in federal funding in 2011, and in January and August 2012, aided a record-breaking number of guests.

According to the 2000 United States Census, Union City had a population of 67,088, making it the second-most populous municipality in the county after Jersey City.

The population density was 52,977.8 inhabitants per square mile (20,395.9/km²) in 2000, approximately twice as high as New York City as a whole, but less than Manhattan alone. Union City is the most densely populated city in the United States, though neighboring Guttenberg (legally incorporated as a town) was more densely populated.

Union City's 2010 population of 66,455 made it the state's 17th largest municipality, having seen a decline of 633 residents (-0.9%) from its population of 67,088 in the 2000 Census, when it was the state's 16th most populous municipality. As of 2010, it was still the country's second-most densely populated incorporated municipality (after the nearby Town of Guttenberg) and the most densely populated U.S. city.

The 2010 United States Census counted 66,455 people, 22,814 households, and 15,514 families in the city. The population density was 51,810.1 per square mile (20,004.0/km²). There were 24,931 housing units at an average density of 19,436.9 per square mile (7,504.6/km²). The racial makeup was 58.01% (38,549) White, 5.25% (3,487) Black or African American, 1.23% (819) Native American, 2.39% (1,587) Asian, 0.05% (33) Pacific Islander, 27.43% (18,231) from other races, and 5.64% (3,749) from two or more races. Hispanic or Latino of any race were 84.71% (56,291) of the population. As of 2010, the city had the highest percentage of Hispanic residents in any municipality in New Jersey.

Of the 22,814 households, 34.2% had children under the age of 18; 36.7% were married couples living together; 21.8% had a female householder with no husband present and 32.0% were non-families. Of all households, 23.8% were made up of individuals and 7.5% had someone living alone who was 65 years of age or older. The average household size was 2.88 and the average family size was 3.39.

23.7% of the population were under the age of 18, 10.6% from 18 to 24, 32.4% from 25 to 44, 22.8% from 45 to 64, and 10.5% who were 65 years of age or older. The median age was 33.9 years. For every 100 females, the population had 100.4 males. For every 100 females ages 18 and older there were 98.3 males.

The Census Bureau's 2006–2010 American Community Survey showed that (in 2010 inflation-adjusted dollars) median household income was $40,173 (with a margin of error of +/− $1,946) and the median family income was $43,101 (+/− $2,185). Males had a median income of $31,987 (+/− $1,696) versus $25,010 (+/− $1,517) for females. The per capita income for the city was $18,506 (+/− $719). About 17.0% of families and 20.0% of the population were below the poverty line, including 29.4% of those under age 18 and 20.8% of those age 65 or over.

Spanish is spoken at home by more than half of the residents of Union City, according to U.S. Census Bureau data released in 2017.

Hispanics remain the dominant ethnic group in the city, and their percentage of the population increased from 82.3% in the 2000 Census to 84.7% in the 2010 Census. Non-Hispanic whites made up 15.3% of the city's population in 2010; up from 13.3% in the 2000 Census. Blacks made up 5.2% of the city's population in 2010; up from 3.3% in the 2000 Census. The rest of the racial makeup of the city was 0.70% Native American, 2.15% Asian, 0.08% Pacific Islander, 28.19% from other races, and 6.87% from two or more races. Though Native Americans comprise less than 1% of the city's population, they doubled between the 2000 and 2010 Census, and combined with West New York's Native Americans, comprise 38% of the county's Native American population.

Immigration from Cuba to Union City began slowly in the late 1940s and early 1950s, when jobs in the local embroidery and textile factories were abundant. By 1955, the city's Cuban population was large enough that Fidel Castro visited Union City to raise money for his revolt against Cuban dictator Fulgencio Batista, though a speech he gave one night at a bar on 26th Street, Le Molino Rojo ("The Red Mill") led to a brawl that resulted in Castro's arrest. Following the Cuban Revolution of 1959, large numbers of Cubans in professional occupations emigrated to Union City, resulting in Union City's status as the nation's second-largest Cuban population, behind Miami, Florida, leading to the nickname "Little Havana on the Hudson". Aspects of the enclave are explored in the 2009 publication The Cubans of Union City: Immigrants and Exiles in a New Jersey Community. In the ensuing decades, Cuban residents spread out to other communities of North Hudson County. West New York, at 19.64%, now has the highest percentage of Cubans in New Jersey, with Union City in second place, with 15.35%. These two municipalities have the highest Cuban population percentage in the United States outside of Florida. Moreover, Union City still boasts the largest Hispanic population percentage in New Jersey, at 84.7% by the 2010 Census. By the early 2000s Union City had become a mix of the Latin and Asian diasporas, with Dominicans cited as the fastest-growing ethnic group, and other groups including Colombians, Ecuadoreans and Salvadorans. Despite the decline in the size of the Cuban population, the major New York City television news outlets will often journey to Union City to interview citizens when developments in Cuba–United States relations occur. As of the 2000 census, 5.94% of Union City's residents identified themselves as being of Ecuadorian ancestry, which was the third highest of any municipality in New Jersey and the seventh highest percentage of Ecuadorian people in any place in the United States with 1,000 or more residents identifying their ancestry. That number increased to 9.23% in the 2010 Census. As of the 2000 Census, 58.7% of the population was foreign born and 21.6% of residents were naturalized citizens, while 13.9% only speak English at home, whereas 80.7% reported that they spoke Spanish at home.

In the city the population was spread out, with 25.3% under the age of 18, 11.0% from 18 to 24, 34.3% from 25 to 44, 19.4% from 45 to 64, and 10.0% who were 65 years of age or older. The median age was 32 years. For every 100 females, there were 100.6 males. For every 100 females age 18 and over, there were 98.8 males.

As of 2000, Union City's employment breakdown is: 27% Manufacturing, 15% Professional, 15% Retail, 8% Transportation, 8% Finance/Insurance/Real Estate, 8% Wholesale Trade, 6% Business and Trade, 5% Construction, 4% Personal Service, 3% Public Administration, 3% Communications, and 1% Entertainment/Recreation^{[citation needed]}

As of the 2000 Census, 17% of the city's employed residents work in New York City.

Of Union City's 24,931 housing units (up 1,190 from the 2000 Census), 2,117 of them, or 8%, were vacant, twice the vacancy rate of the 2000 Census.

The median income for a household in the city was $30,642, and the median income for a family was $32,246. Males had a median income of $25,598 versus $19,794 for females. The per capita income for the city was $13,997. About 18.6% of families and 21.4% of the population were below the poverty line, including 28.3% of those under age 18 and 19.3% of those age 65 or over. The Brookings Institution studies ranked Union City among the 92 most economically depressed localities in the United States, with 18.1% of the population and 27.5% of the children falling below the poverty line. In 1997, the New Jersey Municipal Distress Index, which is based on social, economic, fiscal and physical indicators, ranked Union City as the third most distressed community in the state.