The stylish defender has played just 45 minutes since initially feeling the problem after our draw at Middlesbrough at the end of March.
Ledley reported for duty with England on Sunday but the injury forced him to withdraw on Monday morning.
It's a great shame for the 21-year-old after an outstanding season at club level.
He was an ever-present right up until January, when he was rested by boss Glenn Hoddle after starting our first 28 games.
He only missed one more game before Middlesbrough - therefore playing in 41 of our first 43 fixtures - and his form earned him his first full England cap and a place on the PFA Young Player of the Year shortlist.
Ledley looked set to be a first choice selection in David Platt’s starting line-up but instead he'll now recharge the batteries throughout the summer.
Blackburn's Martin Taylor has replaced Ledley for the tournament that starts in Switzerland on Thursday.
England, who will be based in Basel, will open their campaign against hosts Switzerland in Zurich on Friday evening, and then face Italy in Basel on Monday, May 20 before completing the group stage with another tough fixture against Portugal back in Basel two days later.
Ledley King's Achilles problem has ruled him out of the European Under-21 Championship Finals.