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Walker had reported to England's training base with a fibula injury suffered during Tottenham's friendly against Jamaica in the Bahamas on Thursday and the right-back was released following assessment by Roy Hodgson's medical staff.
"Kyle Walker has withdrawn from the England squad to face Republic of Ireland and Brazil," read an FA statement on Monday.
"Walker reported to St. George's Park with an injury on Sunday, which was assessed by the Club England medical staff.
"The Tottenham Hotspur defender will be unavailable for the upcoming two matches and has returned to his club. There will be no replacement at this time."
It means Liverpool's Glen Johnson is the only regular right-back remaining in Hodgson's squad.
However, England do have the option of using Manchester United's Phil Jones in that role, while Phil Jagielka has also played in that position for his country.
There is some good news about Manchester United striker Danny Welbeck, who is reported to be fine despite also missing Monday's training session at St George's Park.
England face Ireland at Wembley on Wednesday and Brazil in Rio on Sunday.
