Datsyuk also scored in regulation for Detroit, which had dropped an NHL-record 11 straight shootouts dating back to last season.
Tomas Jurco added a goal and an assist and Joakim Andersson and Tomas Tatar scored for Detroit in a preview of this year's NHL Winter Classic Jan. 1 at Michigan Stadium.
Jonas Gustavsson stopped 19-of-23 shots.
Joffrey Lupul provided a goal and an assist for the Maple Leafs, who fell for the sixth time in eight games.
James Reimer started in goal for Toronto but was pulled after allowing three goals on 12 shots in the first period.
Jonathan Bernier turned aside 25-of-26 the rest of the way.