George Williams was born in Houston 'round about 1899, and his vaudeville sparring partner, Bessie Brown, was also born in Texas, roughly four years earlier. In 1918 they began working together as Williams & Brown on the touring entertainment circuit overseen by the Theater Owners and Bookers Association. They played the Putnam Theater in New York the following year with 15-year-old Thomas "Fats" Waller at the piano. Among the earliest African-American vaudeville duos to record for a major label, the team of Williams & Brown made 18 records for Columbia during the years 1923-1926; additionally, Bessie Brown cut four sides on her own in 1924, and Williams racked up 15 titles under his own name between 1923 and 1930, delivering his songs in a strong voice with a tendency toward buzzing vibrato. The Williams & Brown discography is most noteworthy for the participation of various members of Fletcher Henderson's orchestra. Williams & Brown were engaged to perform at Pittsburgh's Star Theater in February 1924 and Williams is believed to have appeared as a solo act at the Sunset in Chicago seven months later. Pittsburgh's public apparently appreciated their routines, as the duo was invited back for return engagements in 1925 and 1926.
Williams spent the late '20s pursuing success as a singing actor. He was seen at Chicago's Grand Theater on several occasions in 1927, and then in Brownskin Models and Ginger Snaps of 1928 at the same venue. Williams appeared in A Night in Spain at the Lafayette in New York during June 1928, then in Happy Go Lucky at Pittsburgh's Elmore Theater six months later. When in January 1929 that show moved to the Chicago Apollo, Williams and Brown were on the bill together, and they were also featured in S'Prise Me and Hot Town at the Alhambra in New York during 1930. Williams made his last known recordings in May of that year, and on one selection demonstrated a hitherto undetected knack for yodeling. Bessie Brown (not to be confused with numerous identically named African-American female blues singers from the same period) quit the scene in 1932, moved to Cincinnati, and lived there until her demise in the early '70s. Williams stubbornly persevered as a vocalist throughout the mid-'30s. His last known engagement was at the Apollo in Harlem in October of 1937, and nothing is known about his subsequent professional activities or what happened to him during the remainder of his life.