Italy grabbed the winner in the 50th minute when midfielder Antonio Candreva outfoxed England left back Leighton Baines and chipped a cross deep into the area for Mario Balotelli to head in from close range at the far post.
England otherwise dominated the second half but could not find a way past back-up keeper Salvatore Sirigu, deputising for the injured Gianluigi Buffon.
Italy are joint top of the group with Costa Rica while England must beat Uruguay in their next game to retain realistic hopes of reaching the last 16.
The result was fair and reflected well on both teams, who did not shirk in high humidity and temperatures that were still 30 Celsius (86 Fahrenheit) at kickoff.
“We played well. It was a hard fought victory but we kept control of the midfield,” Italian manager Cesare Prandelli told reporters.
The Italians started with five men in midfield in a bid to clamp down on fleet-footed English forwards Raheem Sterling, Daniel Sturridge and Danny Welbeck.
England began well but some players, including Wayne Rooney and Baines, had games to forget.
Baines often looked out of his depth with Italy regularly mounting dangerous raids down their right flank and Prandelli`s team took the lead in the 35th minute after a cleverly worked corner.
When the ball was played into Andrea Pirlo the veteran midfielder let it run under his boot and Claudio Marchisio had time to hammer home a 25-metre right-foot shot.
“They caused us a lot of problems down our left-hand side in the first half but we made tweaks at half-time and dealt with it better,” England captain Steven Gerrard said.
England recovered quickly and two minutes later a lovely pass from Sterling sent Rooney haring down the left and his curling cross was met by a sweet half-volley from Sturridge.
Italy, though, came close to scoring again in first-half stoppage time.
Balotelli chipped the ball over goalkeeper Joe Hart, only for Phil Jagielka to head it off the line, and seconds later a clever pass found Candreva alone in the area but he crashed his shot against Hart’s right post.
Sirigu was in good form in the second half, palming away fierce shots from Welbeck and substitute Ross Barkley as well as a free kick from Baines.
“It is a very disappointing result and there is no reason take positives when you have lost,” England manager Roy Hodgson said.
“But my gut feeling is that we did some very good things on the pitch but unfortunately we conceded that second goal.”
England eventually paid the price for their efforts in the heat. Among others, Gerrard and Sturridge went down with cramp.
“It was a tough night. It was warm, sticky – it was a tough pitch – it was dry. But they’re excuses. Italy were very good,” said Gerrard.
Pirlo almost made it 3-1 in second-half stoppage time but his swirling 30-metre free kick crashed against the bar.
The players appeared to have no problems with the pitch, which had been damaged by humidity in the months running up to the tournament and required special repairs.
But Prandelli said it was “madness” not have an officially sanctioned time out in the brutal conditions.
“We had to lower the rhythm to gather breath, it was impossible to keep up that intensity,” he said.
The result was the first World Cup win in four games for Italy, who drew two and lost one of their 2010 matches.
The defeat meant England have not beaten a major nation at the World Cup since a 1-0 win over Argentina in 2002.
(Additional reporting by Zoran Milosavljevic,; editing by Ed Osmond)