The Football Association confirmed on Monday that James had "sustained an injury" in Chelsea's 2-1 win over the champions on Saturday. The full-back had started at right-back before moving to central defence and completing the full 90 minutes.
Manchester City youngster Nico O'Reilly has been called up to replace James, earning his first senior England call-up. The 20-year-old midfielder, who has featured mainly at left-back for Pep Guardiola's side this season, had originally been selected for the England Under-21s.
England are set to face Wales in a friendly at Wembley on Thursday before travelling to Riga for a World Cup qualifier against Latvia on 14 October.
The timing of James' withdrawal is a concern for Chelsea, who are already struggling with a series of absences. Including suspended defender Trevoh Chalobah, the Blues had eight players unavailable for the match against Liverpool.
James has shared right-back duties with Malo Gusto this season but could now face a spell on the sidelines depending on the severity of his injury. Chelsea's medical team have conducted initial assessments and will use the October international break to provide further rest.
The club next play Nottingham Forest in the Premier League on 18 October.
James has been a key figure for England under Thomas Tuchel, scoring his first international goal in March against Latvia and establishing himself as the first-choice right-back "slightly ahead" of Trent Alexander-Arnold, according to the national team manager.
O'Reilly, meanwhile, brings versatility and youth experience. Despite being a midfielder by trade, he has logged significant minutes at left-back this season and has represented England at multiple youth levels, though he has yet to make an appearance for the U21s.
Tuchel had largely retained the squad that defeated Andorra 2-0 and Serbia 5-0 in September, only making injury-related changes, with Bukayo Saka included after Noni Madueke withdrew. "I'm saying there's a chance. It's very likely I wouldn't have (called Saka)," the England manager has said.
Mikel Arteta has described Granit Xhaka as "one of the signings of the season" ahead of Arsenal's reunion with their former midfielder when they face Sunderland at the Stadium of Light on Saturday.
England manager Thomas Tuchel has recalled Jude Bellingham and Phil Foden for next week's World Cup qualifiers against Serbia and Albania, while Bournemouth midfielder Alex Scott earns his first senior call-up.
Strasbourg's on-loan defender Mamadou Sarr has chosen to represent Senegal at international level despite having represented multiple France youth teams.
Jadon Sancho's struggles deepened on Thursday night as the on-loan Manchester United winger failed to seize his opportunity in Aston Villa's 2-0 victory over Maccabi Tel Aviv.
