Labelled as the 'rumble in jungle' heading into the match, Italy continued their domination over England thanks to goals from Claudio Marchisio and Mario Balotelli at the Arena Amazonia.
Daniel Sturridge had England on level terms at half-time, 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 were left with just two wins in their past 12 international meetings against Italy.
Italy are back in action against Costa Rica on Friday, while England face Uruguay a day earlier.
England manager Roy Hodgson made just one change from the team that stuttered to a goalless draw against Honduras in their final warm-up match, with Raheem Sterling free from suspension to replace Adam Lallana in midfield.
It was a different story for Italy, who were forced into two changes.
Captain Gianluigi Buffon failed to overcome an ankle strain and was replaced by Salvatore Sirigu in goal, while full-back Mattia De Sciglio also dropped out through injury and Matteo Darmian took his place in the starting eleven.
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.
Although, 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 who opened the scoring courtesy of Marchisio 11 minutes before the half-time 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's lead was short-lived as their lack of pace in defence was exposed two minutes later.
After a swift counter-attacking 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 champions just five minutes of the second half to restore their 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 leapt 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 equaliser but it was Italy that came closest to a late goal with Pirlo hitting the crossbar with a free-kick in stoppage time, as they emerged triumphant in just their second World Cup clash against England.
