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 Pittsburgh's second shooter in the shootout and missed on a backhand attempt.
The Penguins' Tomas Vokoun and the Blackhawks' Nikolai Khabibulin played the entire game. Vokoun finished with 30 saves through overtime and Khabibulin, who rejoined the Blackhawks as a free agent in the offseason, had 27.
Sharp opened the scoring on a one-timer 5:19 in. Pouliot scored a screened power-play goal midway the first and Vitale connected late in the period to give Pittsburgh a 2-1 lead.
Crosby made it 3-1 at 4:19 of the second, then Smith cut it to 3-2 with short-handed goal midway through the period.
Blackhawks forward Marian Hossa has an upper-body injury and will not be available until the final game of the preseason at the earliest, coach Joel Quenneville said earlier on Thursday.