The luckless Chelsea centreback joins midfielders Gareth Barry and Frank Lampard's, whose hopes of playing in Poland and Ukraine were dashed by injury.
England's injury troubles have deepened with defender Gary Cahill ruled out of the European Championship after fracturing his jaw in the final warm-up match against Belgium.
And veteran defender Rio Ferdinand appears annoyed that he has been snubbed by coach Roy Hodgson as the inexperienced Martin Kelly took Cahill's place in the 23-man squad.
Cahill, the starting centre back, is the third England player in the last week to be ruled out of the tournament, following injuries to midfielders Frank Lampard and Gareth Barry ahead of the June 11 opener against France.
But another central defender, John Terry, has been given the all clear by England's medical staff following fears of a hamstring injury after coming off during Saturday's 1-0 victory, although he will be re-assessed on Tuesday before the squad travels to its Euro 2012 base in Krakow, Poland.
Cahill was forced out with the injury in the first half at Wembley Stadium on Saturday after being shoved into England goalkeeper Joe Hart by Dries Mertens.
"The Chelsea defender has two fractures of his jaw, one either side," the Football Association said. "The England medical team have been in close contact overnight with Cahill's club doctors who will treat him moving forward."
Kelly now returns to the squad to take Cahill's place after initially being a standby member, having only made his England debut a week ago when he came on in the 87th minute of the 1-0 victory over Norway. He made 12 Premier League appearances for Liverpool last season.
Hodgson overlooked Ferdinand, who is more experienced with 81 caps, although injuries and loss of form mean he hasn't played for England since June last year.
"Lampard, Terry, Barry, (captain Steven) Gerrard; all ageing but they go to the tournament," said Jamie Moralee, Ferdinand's representative.
"Why is Rio different? To treat a player that has captained and served his country 81 times (in this manner) is nothing short of disgraceful.
"Total lack of respect from Hodgson and the FA as far as I am concerned."
Ferdinand indicated his annoyance himself on Twitter when he wrote: "What reasons?????!!!"
That appeared to be a reference to Hodgson insisting last month that Ferdinand was not going to Euro 2012 for "football reasons", and not due to fears over a potential conflict with Terry.
Terry is due to stand trial next month on a charge that he racially abused Ferdinand's brother, Queens Park Rangers defender Anton Ferdinand, during a Premier League match in October.
Terry, who denies any wrongdoing, lost the England captaincy over the case, which led to Fabio Capello quitting as coach in February and Hodgson taking charge last month.
Kelly's inclusion means more than a quarter of the 23-man England squad play for Liverpool, with the six players only managing to steer the club to eighth in the Premier League.
