Williams has played in the NHL with the Detroit Red Wings, Chicago Blackhawks, Atlanta Thrashers, Columbus Blue Jackets, Dallas Stars, and the Pittsburgh Penguins.

Returning to the Wings in 2005–06 under new head coach Mike Babcock, Williams broke out with 21 goals and 58 points, frequently playing on a line with Steve Yzerman and Robert Lang.

[3] On November 8, 2006, during a game against the Edmonton Oilers, Williams was injured when he was checked from behind the net by Raffi Torres, causing his head to hit the ice.

After a 36-point season in 43 games with Chicago, Williams became an unrestricted free agent and was signed by the Atlanta Thrashers on July 13, 2008, to a one-year, $2.2 million deal.

[7] Williams performed well with Columbus, scoring 12 goals and 17 assists for the remainder of the 2008–09 season as the Blue Jackets qualified for the playoffs for the first time in their history.

[12] Williams was assigned to AHL affiliate, the Wilkes-Barre/Scranton Penguins, for the majority of the 2011–12 season, however was recalled to produce a goal and assist in an eight-game stint with Pittsburgh.

With limited NHL interest in 2012, Williams opted to resume his career in Europe, agreeing to a two-year contract with the Swiss club, HC Ambrì-Piotta of the National League A.

[13] In the 2014–15 season, Williams provided the Barons with a veteran presence and leadership while showing no loss of his offensive touch with 53 points in 72 games.

On July 16, 2015, Williams made another return to Europe in signing with his first German club, Kölner Haie of the DEL, on a one-year deal.