Born in Waco, Texas, Williams was the lead singer of the Charioteers between 1930 and 1950, when he formed his own Billy Williams Quartet with Eugene Dixon, Claude Riddick and John Ball. Many television appearances followed, including an appearance on Your Show of Shows with Sid Caesar.
On April 5, 1959, the Billy Williams Quartet appeared on the Ed Sullivan show and performed a rousing version of Goodnight Irene.
By the early 1960s he lost his voice due to complications of diabetes. He subsequently moved to Chicago and worked as a social worker until his death there in 1972 at age 61.