PSG has now won the season-opening trophy on 14 separate times.
The Parisian giants needed a dramatic equaliser followed by a successful spot-kick decider to get past their arch-rivals in the Gulf and secure a fourth straight Trophee des Champions victory.
The Champions League holders appeared to be sailing towards a straightforward win in the showdown featuring the French league winners and the Coupe de France holders after the French winger found the scoring in the opening stages.
Yet, Marseille fired two times late to seize a surprise lead. First, Mason Greenwood scored from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a remarkable turn of events, Goncalo Ramos grabbed a crucial equaliser in the dying moments to send the match into a penalty shootout. PSG goalkeeper Lucas Chevalier then stood as the hero, saving crucial attempts from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and the young talent all converted successfully for PSG to seal a convincing penalty win.
Now 14-time winners PSG, who faced last season's Ligue 1 runners-up Marseille after completing a domestic double, have now won this trophy for the 12th time in the last 13 years.
