Sidney Crosby, Derrick Pouliot and Joe Vitale scored in regulation for Pittsburgh (1-1-1).
Chicago's Brandon Bollig shoveled in a rebound from a scrum in front of the net with 6:53 left in the third to tie it at 3 and send it to overtime. Patrick Sharp and Ben Smith both scored for the second straight game for the Blackhawks (1-1-0).
Crosby, whose career has been punctuated by games lost to concussions, was struck by the stick of Chicago's Adam Clendening in the final minute of overtime and dropped to the ice. He got up slowly, then skated to the bench on his own.
Crosby was Pittburgh's second shooter in the shootout and missed on a backhand attempt.