Claudio Marchisio and Mario Balotelli sandwiched a Daniel Sturridge strike to give Cesare Prandelli's men all three points from their opener against Roy Hodgson's charges.
Italy made the perfect start to its FIFA World Cup campaign, topping Group D rival England 2-1 in Manaus on Saturday.
Labelled as the 'rumble in jungle' heading into the match, Italy continued its domination over England thanks to goals from Claudio Marchisio and Mario Balotelli at the Arena Amazonia.
Daniel Sturridge had England on level terms at halftime, after cancelling out Marchisio's 35th-minute opener within two minutes.
But Balotelli repaid the faith shown in him by coach Cesare Prandelli, popping up to head home the winner five minutes after the break as England was left with just two wins in the past 12 international meetings against Italy.
Italy is back in action against Costa Rica on Friday, while England faces Uruguay a day earlier.
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England manager Roy Hodgson made just one change from the team that stuttered to a goalless draw against Honduras in its final warm-up match, with Raheem Sterling free from suspension to replace Adam Lallana in midfield.
It was a different story for Italy, which was forced into two changes. Captain Gianluigi Buffon failed to overcome an ankle strain and was replaced by Salvatore Sirigu in goal, while fullback Mattia De Sciglio also dropped out through injury and Matteo Darmian took his place in the starting team.
Up front, Prandelli decided to stick with wayward striker Balotelli, despite Ciro Immobile's hat trick display against Brazilian club Fluminense midweek.
Much had been said about the weather in Manaus leading into the match but conditions did not affect the early exchanges as both teams pressed forward.
As far as chances were concerned inside the opening 20 minutes, both sides were limited to long-range efforts, with Sterling, Jordan Henderson and Antonio Candreva trying their luck from distance.
England did come close to breaking the deadlock in the 23rd minute, albeit fortuitously, when Danny Welbeck's low pass across the penalty area deflected off Andrea Barzagli and just narrowly wide of the far post with Sturridge lurking.
However, it was Italy which opened the scoring courtesy of Marchisio 11 minutes before the halftime interval after a well-executed short corner.
Candreva passed to Andrea Pirlo on the edge of the box and the veteran midfielder let the ball run through to Marchisio, who fired a low shot past goalkeeper Joe Hart from 25 yards.
The Italian lead was short-lived as the lack of pace in Itlay's defense was exposed two minutes later.
After a swift counterattacking move, Wayne Rooney was freed on the left and delivered an inch-perfect cross for Sturridge to convert on the half volley.
England and Italy went into the break on level terms but it took the four-time world champion just five minutes of the second half to restore the lead, this time thanks to Balotelli.
Candreva was in the thick of the action again, beating Leighton Baines to pick out Balotelli at the back post and the Milan striker got up highest to nod home his first international goal since October last year.
Rooney had a great chance to restore parity and net his first World Cup goal, however, he fluffed his lines inside the penalty area on the hour mark.
Hodgson introduced midfield trio Ross Barkley, Jack Wilshere and Adam Lallana in search of an equalizer but it was Italy that came closest to a late goal with Pirlo hitting the crossbar with a free kick in stoppage time, as the Azzurri emerged triumphant in just their second World Cup clash against England.