Acquired from the Penguins in 1996, Naslund polished off his second career four-goal effort by wristing a shot from the right faceoff dot between the skates of rookie goaltender Marc-Andre Fleury 24 seconds into overtime.
The goal gave the Canucks their fourth straight win over Pittsburgh and improved them to 1-1-1 on their five-game homestand.
Naslund, who also tallied four times against Edmonton Dec. 14, 2002, notched his first hat trick of the season and 10th career 6:08 into the third period, giving Vancouver a 3-2 lead.
Naslund returned to the lineup after missing Saturday's tie with Minnesota with a groin injury.
Milan Kraft knocked his own rebound out of the air and past former Penguin Johan Hedberg with 6:19 left for his second goal of the game, forcing the extra period.