Chelsea boss Emma Hayes made many changes to her starting XI for the encounter at Stamford Bridge but the Blues looked as strong as ever, going on to take the lead just 11 minutes in. It all began when the home team won the ball in the middle of the pitch before it was played through to James, who shimmied past Gemma Bonner and fired into the net.
Liverpool drew level right away, though, when Shanice van de Sanden's low cross was knocked into the net by Chelsea defender Jessica Carter, but the hosts got back on top shortly afterwards with a fantastic cross from James that was met by Aggie Beever-Jones and headed into the net.
Liverpool looked capable of pushing for an equaliser, but James dashed their hopes with two more fine goals in the second half before Sjoeke Nusken tapped in to secure a 5-1 win.