The Italians won through to a semi-final against Germany in Warsaw on Thursday thanks to the winning penalty from Alessandro Diamanti after Ashley Young and Ashley Cole missed for England.
Italy had the better of the chances throughout - a swerving effort from Daniele de Rossi hit the post after just two minutes setting the tone. And they had a goal disallowed late on in extra-time when Antonio Nocerino saw his close-range header chalked off for offside.
England did have their moments and Italy keeper Gigi Buffon made a fine early stop from Glen Johnson. Mario Balotelli then fired a close range effort too close to Joe Hart before Wayne Rooney astutely found Manchester United teammate Danny Welbeck, who leaned into his effort and fired over.
After the restart, England had a let off as Hart saved from De Rossi and Balotelli before Riccardo Montolivo put the rebound over from point blank range.
England threw on Andy Carroll and Theo Walcott for Welbeck and James Milner on the hour in an attempt to regain the initiative in the face of increasing Italian pressure but neither side could find a way through. There were few chances in the first-half of extra-time with Diamanti going closest with a cross hitting the post.