Williams began playing guitar when he was 12. He played in rock bands in high school, and studied with blues musician Johnny Shines from the late 1960s until 1971. In the early 1970s Williams played in the University of Alabama B Jazz Ensemble and the Salt & Pepper Soul Band. He also started working with LaDonna Smith around this time, and founded a musical ensemble and recording project called Transmuseq. He toured the U.S. and Europe in 1978. In the early 1980s he worked in a blues band called Trains in Trouble. In 1986 Williams joined Curlew, who released several albums on Cuneiform Records in the 1990s.
In the 1980s he also worked with Col. Bruce Hampton and OK, Nurse, and in the early 1990s played in a punk rock band called Fuzzy Sons. Williams played in an improvisational three-piece called Say What?, and worked with Jim Staley and Ikue Mori. Williams appeared live at some 1,500 concerts worldwide.
Williams co-founded The Improviser, a journal of experimental music, in 1981. He also worked as a music critic for the Birmingham News and published freelance criticism elsewhere.