James is currently nursing a hamstring injury, but he is suspended anyway after being sent off against Brighton & Hove Albion in the Blues' penultimate match of last season.
Malo Gusto is therefore expected to start at right-back as Marc Cucurella and Ben Chilwell battle for the left-back berth, while Levi Colwill could be partnered at centre-back by Wesley Fofana - who missed the entire 2023-24 campaign through injury - over Axel Disasi, Benoit Badiashile and new signing Tosin Adarabioyo.
After playing regularly in pre-season, Robert Sanchez is expected to start the new season as Enzo Maresca's first-choice goalkeeper, despite the £20.7m arrival of Filip Jorgensen from Villarreal.
In midfield, Maresca has renewed acquaintances with ex-Man City academy star Romeo Lavia, who is poised to make his first Premier League start for Chelsea - 12 months after joining the club following an injury-plagued 2023-24 season - and could link arms in the middle of the pitch with Enzo Fernandez and Moises Caicedo.
New recruit Kiernan Dewsbury-Hall is also in contention to start, but Conor Gallagher is not expected to be involved amid interest from Atletico Madrid.
Last season's top scorer - and another former Man City player - Cole Palmer could operate on either the right or left flank, while the other wide spot is up for grabs, with £60m arrival Pedro Neto set to compete with Raheem Sterling, Mykhaylo Mudryk and Noni Madueke for a start in attack.
Eighteen-year-old Marc Guiu, a summer signing from Barcelona, featured regularly in pre-season, but the striker may have to settle for a place on the substitutes' bench this weekend, as Christopher Nkunku could be tasked with leading the line.
Nicolas Jackson, meanwhile, earned his first minutes of pre-season las weekend after recovering from an ankle problem and should be fit to feature as a substitute.
Chelsea possible starting lineup: Sanchez; Gusto, W. Fofana, Colwill, Cucurella; Fernandez, Lavia, Caicedo; Neto, Nkunku, Palmer