The English international right-back has been forced to withdraw from group training sessions and is now undergoing solitary workouts at the club’s Cobham training Centre.
James had been making strides in his recovery from a hamstring injury he sustained in August.
However, the recent setback has cast doubt over his availability for the crucial clash against Arsenal at Stamford Bridge this weekend.
Malo Gusto is now available to fill in for James after serving a three-match suspension following his red card against Aston Villa last month.
Gusto, who recently made his senior debut for France during the international break, returns to London on Wednesday and could deputise for James.
Marc Cucurella has admirably deputised in the right-back role, providing defensive solidity in James and Gusto’s absence. He could keep his place in the starting line-up.
Armando Broja and Carney Chukwuemeka are also doubtful to feature against Mikel Arteta’s side.
Broja recently returned from a 10-month absence due to knee surgery and is racing against time to secure a spot on the bench after picking up a knock.
Nicolas Jackson is expected to lead the line with a cast on his wrist following minor surgery.
Chukwuemeka is under the medical staff’s scrutiny after experiencing knee pain during full training sessions after returning from an injury lay-off.
Chelsea remain hopeful that Trevoh Chalobah and Benoit Badiashile will soon return from injury.
They have not played a minute this season, with Chalobah suffering an injury in pre-season, while Badiashile has been carrying his problem since the end of last term.
Ben Chilwell, Christopher Nkunku, Romeo Lavia, Wesley Fofana and Marcus Bettinelli are also on the sidelines.
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