When Maresca revealed at Friday's press conference that the club captain was available for selection, the expectation was that he would be selected on the substitutes' bench at best.
Instead, despite the 24-year-old not playing a competitive game all season, the Italian has chosen to use James at right-back and switch Malo Gusto to the left as a replacement for the suspended Marc Cucurella.
Tosin Adarabioyo has taken the spot of Wesley Fofana - who is also serving a one-match ban - in the middle of the backline.
Another bold choice by Maresca is including Romeo Lavia in central midfield ahead of Enzo Fernandez in what is the third and final change. Lavia has not started a Premier League game since August 18.
Mykhaylo Mudryk is one of the players who does not make the bench, despite having made an impact against Nottingham Forest in the previous game.
Slot makes three changes
Meanwhile, Liverpool boss Arne Slot has also made three alterations to his starting lineup, one of them already anticipated due to the injury to goalkeeper Alisson Becker.
Caoimhin Kelleher is named between the sticks, while Andrew Robertson returns at left-back in place of Kostas Tsimikas.
The third and final alteration sees Dominik Szoboszlai come in for Alexis Mac Allister, who was a doubt after playing with an issue for Argentina during the international break.
Liverpool XI: Kelleher; Alexander-Arnold, Van Dijk, Konate, Robertson; Szoboszlai, Jones, Gravenberch; Gakpo, Jota, Salah
Subs: Jaros, Gomez, Endo, Diaz, Nunez, Mac Allister, Tsimikas, Quansah, Morton
Chelsea XI: Sanchez; James, Adarabioyo, Colwill, Gusto; Caicedo, Lavia; Madueke, Palmer, Sancho; Jackson
Subs: Bettinelli, Disasi, Badiashile, Veiga, Fernandez, Dewsbury-Hall, Neto, Joao Felix, Nkunku