Pascal Dupuis scored a pair of late goals to lift Pittsburgh over Toronto, 3-1, at Air Canada Centre.
Craig Adams also tallied, while Chris Kunitz posted two assists for the Penguins, who upped their league-best road record to 12-4-0 by extending their season-high win streak to seven games.
Marc-Andre Fleury snagged the win with 28 stops.
Tyler Bozak picked up the lone score for the Maple Leafs, losers in four straight. Ben Scrivens made 25 saves in defeat.
"Fundamentally, we had some breakdowns which cost us the hockey game," said Leafs head coach Randy Carlyle. "For 53 minutes we did a lot of things really well, but they scored two goals which were flaws of defensive coverage."
As it did on Tuesday on home ice against Boston, Pittsburgh tallied three times in the final minutes to steal a victory.
The visitors knotted the score with 7:18 left in regulation, as Kunitz beat his man to a puck along the boards, and dished to Sidney Crosby, who slid a blind, backhand pass across the slot to Dupuis for the goal.
"A great play by Sid. Around the back, no-looker, he finds me back door with an empty cage and I just got to put it in," Dupuis noted.
Fleury made a glove save on a Leo Komarov breakaway with 3 1/2 minutes to play, then Dupuis one-timed a Kunitz feed in the slot and the Penguins were up 2-1 with 2:10 on the clock.
"Unbelievable play by Chris. Drives dman all the way deep in their zone. Tight turn, finds me there in the slot," said Dupuis of the go-ahead tally.
Scrivens was called to the bench for an extra skater with over a minute to go, and Pens rearguard Brooks Orpik was sent off for boarding with 22.4 ticks left.
Adams iced the game when his clearing attempt from the Leafs' zone rolled into the empty net.
Toronto hit the scoreboard one second after the midway point of regulation, as Bozak finished off a passing play with a sharp-angle goal from the left side.
Phil Kessel brought the puck into the zone on the left wing, dished across to Cody Franson, who whipped the disc back across the slot to the goal scorer.
The Penguins took two of three in the season series from the Leafs, also winning 5-4 in a shootout in Ontario five days ago ... Toronto defenseman John-Michael Liles returned to the lineup after 12 games as a healthy scratch, having been out since Feb. 16 ... The Leafs fell to 6-6-1 on home ice this season ... Crosby now has 19 goals and 38 points in 25 career games against Toronto.