Marie-Philip Poulin played hero yet again Saturday night after some trial and error.

The Montreal Victoire captain scored the shootout winner in a 4-3 win over the Ottawa Charge in a thrilling PWHL season-opener for both teams.

Poulin, who was otherwise held off the scoresheet, missed a breakaway in the dying seconds of overtime and another attempt earlier in the shootout.

Head coach Kori Cheverie was confident the third time would be the charm when she sent her superstar out again in the fifth round.

"We did the math quickly, and she's not going to miss three in a row," Cheverie said. "I just did some quick math in my head on that one."

Poulin deked to the forehand and finally beat Ottawa netminder Emerance Maschmeyer low to the blocker side as a raucous 10,033 towel-waving fans at Place Bell exploded out of their seats. Victoire goalie Ann-Renee Desbiens then denied Katerina Mrazova to secure the victory.

"When you go for your third time, you don't want to let your team down honestly," Poulin said. "It did feel good to score that one and to be able to have Ann also backing us up... she had a great game as well.

"To get that first win, it feels good to be at home, getting to have that shootout win. We just gotta keep going and don't take it for granted."

WATCH | Captain Clutch comes through again:

Victoire edge Charge with Marie-Philip Poulin's shootout winner

Marie-Philip Poulin scores the lone shootout goal to lift Montreal to a 4-3 victory over Ottawa.

Poulin's winner spoiled a 42-save performance from Maschmeyer, who held the Charge in the game all night.

The 33-year-old Poulin is known as "Captain Clutch" for shining in the biggest moments, including game-winning goals for Canada in three Olympic gold-medal games.

When Poulin powered her way to a breakaway after a strong backcheck in overtime, Maschmeyer thought she'd seen this movie before.

"It's classic. Classic Pou, she would get that opportunity with seconds to go," Maschmeyer said. "But nothing better, and it's exactly what I'm sure the crowd wanted to see. And for me, what better challenge to go against the best player in the world."

Maschmeyer won that showdown before thwarting Poulin again in the first shootout attempt, but didn't find a silver lining in making her opponent work for the winner.

"I want three [saves]," Maschmeyer said. "But she's a great player. She can do anything. It's always fun to go up against her. And I love the challenge. I hope she thinks I'm a challenge too."

Poulin was denied a couple opportunities to live up to her moniker during the PWHL's inaugural season.

She appeared to score the overtime winner in an emotional Montreal home-opener against Boston on Jan. 13, only for the goal to be overturned in an eventual 3-2 loss. A couple weeks later, she forced overtime with a spectacular goal late against Toronto, but scored just once in four shootout attempts as Montreal fell 4-3.

WATCH | Fans buzzing over Victoire:

Fans are buzzing with anticipation over what Montreal Victoire will bring to PWHL's 2nd season

CBC's Kwabena Oduro spoke to Montrealers who are eager to see what their team has in store for the second season of the Professional Women's Hockey League.

This time, she pulled it off.

"Pou is an emotional player, and she wants to be the contributor that historically she is," Cheverie said. "Throughout the game she was just a little bit frustrated at times with herself and wanting to bury a couple of opportunities.

"She's someone who has the hardest matchups every single game. There's people slashing her, there's people all over her. So when you get to score in that moment, it's a little bit of a relief."

Goalie Maschmeyer 'gave us an opportunity to win'

The Victoire dominated in shots on net by a 36-19 margin through two periods, but Maschmeyer stood tall. Ottawa's netminder thwarted 19 in the first period and Ottawa jumped to a two-goal lead despite getting thoroughly outplayed.

"Tremendous, right? She holds us in there for a lot of the game and gave us an opportunity to win," head coach Carla MacLeod said. "Fell a little short on that side of it, but certainly earned a point. It's nice for her to get that start. Really proud of her effort."

Maschmeyer posted a .915 save percentage playing a league-high 23 games last season.

Depth questions answered

Depth was one of the biggest questions surrounding Montreal after Poulin, Erin Ambrose and Laura Stacey, among others, stacked up an exorbitant amount of ice time during the playoffs while those deeper down the lineup barely saw the ice.

They've answered those concerns for now. Third-round draft pick Abigail Boreen scored in the second period to get Montreal on the board. In the third, second-round pick Jennifer Gardiner tied the game at 3-3 with the Victoire's second unit starting on the power play.

"If you look at all four lines tonight, not only did they create opportunities, but they drew a lot of penalties at the same time," Ambrose said. "And that was a huge power-play goal for us, like, straight up. It's pretty exciting."