James Neal and Sidney Crosby scored in the shootout, leading Pittsburgh over Toronto, 5-4, at Air Canada Centre.
Neal finished the first round with a shot between the pads of Leafs goaltender James Reimer, and after Marc-Andre Fleury flashed his pad to stop Nazem Kadri, Crosby ended the game with a high wrister.
"I wasn't happy giving up four goals, so I wanted to make sure we got those two points at the end," said Fleury.
Neal, Paul Martin, Crosby and Pascal Dupuis tallied in regulation for the Penguins, who ran their road record to 11-4-0 this season thanks to their fourth straight win overall.
Fleury did just enough for the win, recording 22 saves.
Phil Kessel totaled a goal and two assists for the Maple Leafs, losers of two in a row after winning three straight. Clarke MacArthur, James van Riemsdyk and Cody Franson also scored.
Dion Phaneuf added three helpers, but Reimer suffered the loss despite 37 stops.
"This was an intense battle because they're a great team," said Kessel. "We were able to battle back and get a point and that's something positive to take from this."
Neal fired home a loose puck from between the circles only 36 seconds after the opening faceoff.
Van Riemsdyk evened the score just 12 seconds into Toronto's first power play, tipping in a Kessel shot which was threaded through traffic and past Fleury at 7:14.
Crosby picked up a rebound and beat a diving Reimer for a 2-1 game with 5:29 on the clock, and Martin lit the lamp for a two-goal margin 50 seconds later.
Franson's slapper through traffic just after the midway point of the second period brought the Leafs within a goal, but a Dupuis wraparound found the net at 13:01 to restore Pittsburgh's two-goal edge.
Only 60 seconds later, MacArthur beat Fleury to the far post from the left circle.
Toronto pushed the game into an extra session after Kessel's shot hit the back of the net with 4:20 left in regulation.
Pittsburgh improved to 2-0 in the shootout, while Toronto dropped its first foray into the shootout this season ... Kessel tied a season-high with three points ... Pens defenseman Kris Letang ended up with two helpers ... Leafs forward Matt Frattin returned for the first time since Feb. 11, missing 10 games with a knee injury.