Italy's Claudio Marchisio put Italy 1-0 up in the first half, in the 35th minute, only for Daniel Andre Sturridge to score for England two minutes later.
Mario Balotelli secured victory for his side just five minutes into the second half of the game, held in the rainforest city of Manaus.
The Group D match was the first competitive encounter between the teams since Italy beat England on penalties in the quarter-finals of the 2012 European Championship.
In August last year, England edged Italy 2-1 in a friendly.
Joe Hart; Glen Johnson, Gary Cahill, Phil Jagielka, Leighton Baines; Steven Gerrard (capt), Jordan Henderson; Raheem Sterling, Wayne Rooney, Danny Welbeck; Daniel Sturridge
Coach: Roy Hodgson
Salvatore Sirigu; Matteo Darmian, Andrea Barzagli, Gabriel Paletta, Giorgio Chiellini; Daniele De Rossi; Antonio Candreva, Andrea Pirlo (capt), Marco Verratti, Claudio Marchisio; Mario Balotelli
Coach: Cesare Prandelli