Early in his professional career, Williams earned three NBA Finals rings as he contributed off the bench during the Chicago Bulls' first three-peat championships from 1991 to 1993.

On 7 June 1991, in game 3 of the Finals against the Los Angeles Lakers, he scored four points (all from the free throw line), grabbed two rebounds, and had two assists in only 11 minutes of play, in an eventual 104–96 overtime Bulls win.

[7][8] Until his retirement in 2005, at the age of 37, he also played for the Denver Nuggets, the Phoenix Suns (one ½ seasons), the Dallas Mavericks (27 games), and the Cleveland Cavaliers.

[9] Williams is also one of four players to be teammates of Michael Jordan and LeBron James (Brendan Haywood, Larry Hughes and Jerry Stackhouse).

[10] Subsequently, Williams accepted the Cavaliers' offer to become a color commentator for the team's telecasts on FSN Ohio, beginning in 2005–06, and working alongside Michael Reghi.

As of the 2014–15 season, Williams serves as the analyst for Grand Canyon Antelopes men's basketball games on Fox 10 Extra, alongside play-by-play announcer Barry Buetel.

In 2020, on the 'Sixers Talk' podcast, Williams credited Michael Jordan and the Chicago Bulls with helping him have an NBA career.