Williams was signed as an undrafted free agent by the Detroit Red Wings on September 18, 2000. Williams's role on the team was, during his first three years, primarily that of a healthy scratch, getting penciled in only occasionally in place of injured players or when regulars were getting a day off. This changed, however, under new head coach Mike Babcock, and Williams became an everyday player during the 2005-06 season, frequently playing on a line with Steve Yzerman and Robert Lang. He was selected for the Canadian squad for the 2006 World Championships. He won a Stanley Cup with Detroit in 2002.

 

On October 22, 2005, Williams notched his first career hat trick in a 6-0 win over the Columbus Blue Jackets. All three goals came in the first period of that game; it was the first time a Red Wings player scored three times in a single period since Darren McCarty's hat trick in the third period of game one against the Colorado Avalanche in the 2002 Western Conference Finals.

 

Williams re-signed with Detroit on a new two-year contract worth $3.2 million. Williams was acquired by the Chicago Blackhawks on February 26, 2007 in a three way trade with the Philadelphia Flyers and Detroit Red Wings, seeing a 3rd round draft pick and Lasse Kukkonen to the Philadelphia Flyers from the Chicago Blackhawks for Kyle Calder and the Blackhawks trading Kyle Calder to the Red Wings for Williams.