The Parisian club has now won the season-opening trophy on 14 different times.
The Parisian giants needed a dramatic equaliser followed by a perfect spot-kick decider to overcome Marseille in the Gulf and secure a fourth straight Trophee des Champions victory.
The Champions League holders appeared to be coasting towards a comfortable win in the showdown between the French league champions and the Coupe de France winners after the French winger opened the net in the opening stages.
Yet, the southern French side struck two times late to take a surprise lead. Initially, Mason Greenwood scored from the penalty spot, before Willian Pacho inadvertently directed the ball into his own net for an own-goal.
In a breathtaking turn of fortune, Goncalo Ramos snatched a crucial leveler in the dying seconds to force the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the hero, stopping decisive attempts from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all converted with composure for Paris Saint-Germain to complete a convincing penalty victory.
Now 14-time winners PSG, who faced last season's Ligue 1 runners-up Olympique de Marseille after completing a domestic double, have now won this competition for the 12th time in the last 13 seasons.
