The veteran hurt his ankle in training and has failed to recover in time to face Roy Hodgson's men in the two sides' opening World Cup fixture.
Italy has been dealt a severe blow ahead of its World Cup opener against England after goalkeeper Gianluigi Buffon was ruled out with an ankle injury.
The 36-year-old left training early on Friday with the problem, but it was hoped he would recover in time to take his place on Saturday evening, with coach Cesare Prandelli describing it as "nothing serious".
However, Buffon confirmed on his official Facebook page on Saturday that he would not be fit to start the game.PHOTOS: Opening ceremony | Brazil protests | Soccer fanatics | Fan tattoos
Paris Saint-Germain keeper Salvatore Sirigu is expected to start in his absence as the Azzurri look to get off to a flying start in Group D.
One positive for Prandelli, however, was the condition of the playing surface in Manaus, with a close inspection arresting fears of an uneven pitch that had been reported in the days leading up to the game.
"Regarding the pitch, the grass was described to me as being in very bad condition, but when I got here it was actually very good," said the 56-year-old.
Prandelli will keep his formation and selection a secret until the last minute, hoping to keep players competing for places.
He believes Roy Hodgson's England is a different prospect to the one Italy overcame on penalties in the Euro 2012 quarterfinals.
"Two years ago we won on penalties but England are a different team, they have changed their system, their style of play," Prandelli said.
"We have to remember the good things we did in the past but we are facing a new team. Especially in attack, they have four players who are very, very good."