Emma Hayes’ unbeaten aspect had already certified for the knockout section and easily wanted to keep away from defeat to their French opponents by two or extra objectives to lock up their place.
Sam Kerr opened the scoring late in a close-fought first half, which noticed the perimeters get pleasure from an excellent break up of possession.
However the momentum shifted within the hosts’ favour after the restart when James, who had threatened all through the opening interval, netted two in seven minutes at hand her aspect the comfy victory.
The Blues’ remaining group-stage match marked the primary time since 2016 that Chelsea had taken on European competitors on the Premier League venue.
Sandy Baltimore fired PSG’s first likelihood broad of the best publish and Kadeisha Buchanan did properly to stop Kadidiatou Diani from changing an aggressive run down the left channel into any actual alternative.
Moments later, Diani practically handed the guests the lead when she unleashed an effort from distance however caught the crossbar.
Chelsea labored their manner again up the pitch, Fran Kirby chasing the ball down down on the byline and sending a cross to the far publish within the course of James, who caught out her proper leg however couldn’t get a foot on it to drive in an opener.
The Blues began to settle in and James deftly dodged a number of PSG shirts earlier than bouncing a shot within the course of a diving Sarah Bouhaddi on the close to publish.
James tried once more, profitable a battle together with her marker on the left of the realm earlier than charging in and rolling an try throughout the face of aim.
A goalless first half appeared more and more doubtless till the ball skipped simply previous Sakina Karchaoui and PSG didn’t clear. Kerr broke free, neatly transferring the ball from her proper to left foot earlier than unfurling an unstoppable effort into the highest proper nook.
Either side appeared aggressive to start out the second half however Bouhaddi bungled a go to her team-mate, as a substitute directing it into the trail of James who was in a position to toe it to Fran Kirby.
One other fast contact from Kerr completely arrange James, who fired previous the PSG keeper from the sting of the six-yard field for her first Champions League aim.
It took her simply seven minutes to bag her brace after a well-worked passing sequence resulted in a perfectly-placed contact from Kirby on the left of the realm to tee up James’ composed second strike.
Kirby practically arrange a late fourth for the Blues however substitute Beth England directed her effort simply off beam, eliciting a puff however not a aim as the sport drew to a detailed.