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On November 14, 1914, the club was founded. On May 22, 1921, União Barbarense's stadium was inaugurated. In 1921, the team affiliated to APEA (Associação Paulista de Esportes Atléticos, "Paulista Association of Athletic Sports") and played their first match in São Paulo State's Campeonato Oficial de Futebol Amador (Amateur Football Official Championship"). In 1948, the club was Amateur FPF (Federação Paulista de Futebol) champion of its Region.

In 1956, União Barbarense took a leave of FPF's Championship. In 1957, the club was Amateur champion of Liga Barbarense de Futebol ("Barbarense Football League")'s Barbarense Championship. In 1961, União Barbarense was amateur champion of Liga Barbarense de Futebol's Taça Cidade. In 1963, the team was amateur champion of the last edition of Liga Barbarense de Futebol's Taça Cidade.

In 1964, the club affiliated to FPF, became a professional club and competed in the Campeonato Paulista. In 1966, União Barbarense was promoted to Campeonato Paulista Second Division. In 1967, the club was promoted to Campeonato Paulista First Division, just one division below the Special Division. In 1968, União Barbarense competed in the Campeonato Paulista First Division.

In 1972, the club took a leave of FPF's Championship, returning in the following year. In 1974, União Barbarense finished in Campeonato Paulista First Division's fourth place (there was no promotion to the Special Division in that year). In 1975, the club finished in Campeonato Paulista First Division's third place (there was no promotion to the Special Division in that year). In 1977 and 1978, the club was not included in the Intermediate Division, created in 1977, so, União Barbarense did not play in any FPF competition.

In 1979, União Barbarense returned to play in FPF competitions. The team competed in the Campeonato Paulista Third Division. The Third Division, besides its name, was actually the fifth level of Campeonato Paulista. In 1980, the FPF created a Second Division and promoted Barbarense to this division.

In 1990, the club was Campeonato Paulista Second Division's runner-up, returning to the Intermediate Division. In 1991, União Barbarense competed in the Campeonato Paulista Intermediate Division. In 1994, the FPF restructured the Paulista competitions in A-1 (first level), A-2 (second level) and A-3 (third level). União Barbarense was placed in A-3 and finished in tenth place. In 1995, União Barbarense took a leave of Campeonato Paulista A-3. In the same year, Antônio Guimarães Stadium was expanded and modernized.

In 1996, União Barbarense competed again in the Campeonato Paulista A-3. In 1997, The club was Campeonato Paulista A-3's runner-up, and was promoted to the following year's A-2. In 1998, União Barbarense was A-2 champion, thus being promoted to the following year's Campeonato Paulista First Division. In 1999 the club competed in the Campeonato Paulista First Division for the first time.

In 2004, União Barbarense was Campeonato Brasileiro Third Division champion, and was promoted to Campeonato Brasileiro Second Division. In 2005, the club was relegated to Campeonato Paulista Second Division (A-2). In 2005, União Barbarense was relegated to Campeonato Brasileiro Third Division, after ending the league in 20th.