Desperately nervy for an hour, Payet was France's most dangerous player throughout and after creating the opener for Olivier Giroud he finished the job following Bogdan Stancu’s equalizer from the spot.
Romania had started strongly, with Hugo Lloris pulling out a great save from Stancu after just three minutes.
Antoine Griezmann disappointed, despite two good chances in the first half, hitting the post on the quarter-hour in a goalless first half.
Stancu had another chance early in the second half, before Paul Pogba's fizzing volley was beaten away by Ciprian Tatarusanu.
From the resulting corner Payet found Giroud, who outmuscled the Romanian goalkeeper to nod home the tournament's first goal.
That should have been the moment to calm French nerves but instead a mistake from Evra, clipping Nicolae Stanciu in the box six minutes later, allowed Stancu to level matters firing past Lloris.
Just as it looked as though France would have to settle for a point, Payet stepped up and hammered a stunning left-footed strike past a stranded Tatasuranu.
STATS
France 2
Giroud 57, Payet 89
Romania 1
Stancu 64
Referee: Viktor Kassai 7/10
Match rating 3/5
Star man: Dimitri Payet (France)
France: (4-3-3): Lloris 8, Sagna 6, Rami 5, Koscielny 6, Evra 4, Kante 8, Pogba 6 (Martial 76 6), Matuidi 6, Payet 9 (Sissoko 90 N/A), Griezmann 5 (Coman 65 7), Giroud 6
Romania: (4-5-1): Tatarusanu 6, Sapunaru 8, Grigore 6, Chiriches 5, Rat 6, Hoban 6, Pintilii 7, Stanciu 7 (Chipciu 71 6), Popa 7 (Torje 81 7), Stancu 7, Andone 8 (Alibec 61 6)
Sportsbeat 2016
Source: Sportsbeat
