James, who has been struggling with a hamstring injury, will return to his club for further assessment.
This comes after he missed the World Cup due to a knee injury.
The defender played for only five minutes in England's 2-1 win over Italy, which was a friendly match, after coming on as a late substitute.
England has clarified that they will not be calling up any replacements for James or for the suspended Luke Shaw, as the rest of the squad continues their preparations at Tottenham Hotspur Training Ground.
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