The 19-year-old midfielder scored the winner in the 88th minute with a stunning left foot strike to break the 1-1 deadlock and launch France’s campaign in style at the Stade de France on Friday night.
Payet was also instrumental in his side’s first goal as Olivier Giroud headed his cross into the net giving France a 1-0 lead in the 57th minute.
However, Romania struck back in less than 10 minutes as Bogdan Stancu, who was brought down by Patrice Evra in the box, scored from the penalty spot.
Just when it looked the match was heading for a draw, Payet unleashed a powerful left foot drive that found the top left corner.
France made a nervous start to the match as Romania came close to scoring within just five minutes after the start.
A Romanian corner was flicked on by Florin Andone to the back post where Bogdan Stancu's effort from point-blank range was blocked by France’s goalkeeper Hugo Lloris.
The French players soon started applying pressure and created couple of good chances.
Giroud flashed a header just wide from Payet's cross before Griezmann nodded a loose ball against the bar from a narrow angle.
Griezmann again came close to scoring. However, his left foot drive, which looked goal-bound, was deflected by a Romanian defender wide of the goal post.
French coach Didier Deschamps said his team had trouble getting out of the blocks. “But it’s good to get the first game out of the way and to win,” he said.
In Saturday’s matches, England face Russia, Albania take on Switzerland while Wales square off against Slovakia.