Payet played chief tormentor at the Stade de France as he set up Olivier Giroud for the opening goal after the break and then curled a superb left-footer into the top corner of the net with one minute left after Bogdan Stancu had equalised for Romania.
After dominating their opponents in the warm-up friendlies, Didier Deschamps' team failed to ignite in the first half of their first competitive match for two years.
They looked set for a draw in the opening match of the tournament until Payet took the ball on the right flank, cut inside and struck a venemous drive to send the crowd into raptures.
The West Ham United midfielder, who was not even certain of a place in the France squad a few months ago, walked off the pitch in tears and was given an ovation by the crowd after delivering a world-class performance.
"Romania made it difficult for us and it took us time to get into the game especially as there was a lot of emotion," said Payet.
"To be here tonight and score is the result of a lot of hard work and a lot of sacrifices. I wouldn't have thought at the start of the season that I'd be here, there was some pressure on arriving at the stadium but I came to enjoy myself."
France made a shaky start with keeper Hugo Lloris saving well from Stancu at the far post in the fourth minute.
A reaction finally came in the 11th minute when Giroud's header from a Payet cross went just wide.
Lacking the speed and goal instinct that helped them net 13 times in their four previous matches, Les Bleus were a pale shadow of the side who breezed past their recent opponents.
France supporters react during the France v Romania EURO 2016 Group A soccer match, at a fan zone in Marseille, France, June 10, 2016. REUTERS/Yves Herman |
A few chances
Facing a defence that conceded just twice in the qualifiers, France created a few chances though.
A Bacary Sagna cross bounced off Vlad Chiriches' chest into the path of Antoine Griezmann whose header from point-blank range smashed into keeper Ciprian Tatarusanu's left post.
Payet then whizzed down the right flank and Griezmann latched on to his centre but it took a slight deflection and went narrowly wide.
On the stroke of halftime Giroud's header from Payet's corner went just over the bar.
France's first shot on target came seven minutes into the second half, Giroud's low shot from a clever Payet through ball being blocked by Tatarusanu who then parried a powerful 18-metre volley by Paul Pogba.
In the 57th minute Payet sent a cross into the box, the Romanian keeper flapped weakly at the ball and Giroud headed it under the bar for his eighth goal in six internationals.
Eight minutes later Stancu was handed the chance to level after Patrice Evra's silly foul on Nicolae Stanciu and, facing the Romania fans behind Lloris' goal, calmly slotted home.
Deschamps replaced Griezmann with the speedy Kingsley Coman and the disappointing Pogba with Anthony Martial but the two youngsters made little impact.
"It wasn't easy to play this Romanian team," said Deschamps. "We had chances but gave them some too.
"It was difficult to ... relax but it's important to win the first match. The opening game is never easy and it's a great platform."
France, who are top of the table with three points, next take on Albania on Wednesday.