A 1-1 draw after 90 minutes meant the tie would have to be decided on penalties with Timo Werner’s goal cancelled out by Cameron Archer.
Chelsea already had the advantage of winning the European Super Cup in a shootout at the start of the season and repeated that feat at Stamford Bridge.
But it came down to the final kick with James’ strike securing a 4-3 win.
James Robson was at Stamford Bridge to rate the Chelsea players…
Wonder save denied Archer when Villa had the chance to open the scoring just before the break. Saved one spot-kick in the shootout to give Chelsea the advantage.
Influential at both ends. His goal-line clearance stopped Anwar El Ghazi’s effort, then it was his cross to Werner that opened the scoring. Then planted the winning spot-kick.
Stepped up well to win balls early and strong in the challenge but stretched as Villa applied the pressure in the second half.
Booked for a reckless lunge, but was generally confident in what he did and stood up well to the physical challenge.
Should have done better from some of his crossing positions in the first half particularly, but a threat out wide.
Seemed like an odd decision to start him in this game and he was taken off at half-time without dominating midfield in the manner we’ve come to expect from him.
Another tough night against Villa for the loan signing. He looks a long way off finding his feet at Chelsea.
Good minutes and a good test. Pushed up high, but Chelsea did not see enough of his crossing ability.
Had his moments, both with efforts on goal and his crossing. One of Chelsea’s more threatening players.
A goal at last but he really should have done better when through on goal moments later. Still a work in progress, but his confidence should be lifted by scoring.
Moments of elegance and drive – particularly with one first-half run that Chelsea should have done more with. He can be of value this season.
Mason Mount (Kante, 46’) 7
Made a difference when he came on, giving Chelsea more thrust and had a couple of decent chances too.
Romelu Lukaku (Saul, 76’) 5
Gave Villa something else to worry about, but was never found by his Chelsea team-mates.
Ross Barkley (Ziyech, 76’) 5
Bright and put himself about to add more energy to Chelsea’s midfield.
Subs not used: Bettinelli, Mbuyamba, Thiago Silva, Havertz