A second-half strike from France substitute Bafetimbi Gomis saw his side come from a goal down to win 2-1 and chalk up their first triumph on Italian soil since 1994.
Lyon striker Gomis poked a shot home after 67 minutes following a low ball in from Patrice Evra to turn the game around.
Italy were dominant for much of the first half and took the lead through Stephan El Shaarawy, who ran through the middle to fire past Hugo Lloris from Riccardo Montolivio’s through pass - but the advantage lasted only two minutes as Mathieu Valbuena conjured up a brilliant equaliser.
Valbuena evaded his markers on the left and cut into the Italian penalty area before firing an unstoppable shot across goalkeeper Salvatore Sirigu and high into the top corner.
Both sides had lined up in initial 4-3-3 formations and home coach Cesare Prandelli, as he had promised, took the opportunity to rest some of his regulars and played a front three of Mario Balotelli, El Shaarawy and Antonio Candreva.
Balotelli exemplified Italy’s determined start to the match and the extrovert Manchester City man fired an early warning, blasting the ball over the top from the edge of the area with the first real effort of the evening.
Moments after that, the Italy striker came agonisingly close to a breakthrough when he hit the angle of post and crossbar after El Shaarawy, battling well, had laid the ball back to him 25 yards out and his beautifully-struck effort had Lloris comprehensively beaten.
And Euro 2012 semi-final hero Balotelli – who had been challenged by Prandelli to show that he was now "a mature footballer" - was involved again when the Italians broke through as his neat lay-off gave Montolivio the chance to put El Shaarawy through on goal.
But after the equaliser, the Italians appeared shocked and - a deflected Balotelli effort apart - failed to string much together for the remainder of the half.
Prandelli brought playmaker Andrea Pirlo into the action at the start of the second period - one of a flurry of second-half substitutions - but his side were unable to stop France from increasing their attacking threat as the game wore on.
The visitors could have added to their advantage as substitute Jeremy Menez saw his low shot touched around the post, while Italy came close to a leveller when Emanuele Giaccherini hit the crossbar with a well-hit effort from the edge of the penalty area.
MAN OF THE MATCH
Stephan El Shaarawy - Italy: Although substituted towards the end, the Milan player revelled in his role as part of his country's front three. He gave the France defence little respite and, in addition to his cool finish, kept things moving with a repertoire of neat touches and intelligent runs.
Italy: Sirigu 7, Maggio 6, Barzagli 7, Chiellini 6, Balzaretti 6, Montolivo 7, Verratti 7, Marchisio 6, Candreva 6, El Shaarawy 8, Balotelli 7. Subs: Giovinco 7, Bonucci 6, Pirlo 6, Diamanti 7, Giaccherini 6, Florenzi 6.
France: Lloris 7, Debuchy 7, Sakho 8, Koscielny 6, Evra 7, Capoue 6, Sissoko 6, Valbuena 7, Matuidi 6, Giroud 5, Ribery 6. SubsReveillere 6, Menez 7, Gonalons 6, Gomis 6, Gourcuff 7, Tremoulinas n/a.