After being eliminated from Euro 2012 by the Azzurri, Roy Hodgson's side get the new campaign underway with a victory thanks to the Tottenham man's stunning strike
Italy captain Daniele De Rossi's header gave his side the lead before Phil Jagielka equalized with a similar effort. The Three Lions' victory was completed by Jermain Defoe's stunning 25-yard effort.
Jack Butland and Tom Cleverley made their senior international debuts from the start, the former becoming England's youngest-ever goalkeeper in the process, while the returning Michael Carrick and Frank Lampard lined up alongside the Manchester United man in the center.
The Azzurri also included a debutant pairing in attack, AC Milan's Stephan El Shaarawy and Mattia Destro, recently signed by Roma, making their bow for Cesare Prandelli's side.
In a quiet opening, the best chances were found from set-pieces, including Angelo Ogbonna's thumping a header over in the opening minutes, while Andy Carroll also got too much on his headed effort from Lampard's corner.
The Azzurri took the lead on 15 minutes, again from a set-piece. Alessandro Diamanti's corner was drifted into the center and De Rossi lost Carrick before flicking his header over Butland and into the net.
Hodgson's men continued to press, however, and grabbed an equalizer just before the half-hour through Jagielka as the Everton man's diving header from Lampard's corner zipped into the net with no man on the post for the Italians.
England looked energized after the goal. A flowing move between Young and Cleverley found Lampard, who forced Sirigu into a smart save from distance, but Butland had to be alert to turn away Diamanti's dangerous cross with Destro again lurking.
Substitutions were predictably seen at halftime with Defoe and John Ruddy replacing Carroll and Butland for England while Atalanta's Federico Peluso came on for his Italy debut in place of Balzaretti.
Destro forced a good save out of Ruddy with a low effort and the forward's grit was again on show as he blustered his way into the area only being denied by a last-ditch Cahill challenge that fell to Aquilani but the former Liverpool man's ball to Abate was poor and the chance was wasted.
A trio of debutants were introduced by the Azzurri as Manolo Gabbiadini, Andrea Poli and Paris Saint-Germain new boy Marco Varratti came on in place of El Shaarawy, Aquilani and Diamanti while James Milner and Joleon Lescott also came on for Young and Jagielka as Hodgson looked to inject impetus into the Three Lions.
Ryan Bertrand was brought on for Baines for his senior England bow and was immediately called upon to hack the ball off the line from an Italian corner.
In an instant, England burst up the other end with Defoe found in the channel. With few available, the Tottenham striker cut inside and unleashed a swerving shot from the corner of the box that Sirigu could only palm into the net.
The Azzurri had half-hearted shouts for a penalty turned down as Abate's shot deflected up onto Lescott's midriff, with the Italians claiming in vain for a handball.
Defoe was close to notching another in stoppage time, but Astori was on hand to turn away Milner's cross with the Tottenham man awaiting a tap-in and the Three Lions held on for their first win over Italy since 1997.