The Parisian club has now claimed the season-opening cup on 14 different occasions.
Paris Saint-Germain required a stoppage-time equaliser followed by a successful spot-kick decider to overcome their arch-rivals in the Gulf and secure a fourth straight Trophee des Champions victory.
The Champions League holders seemed to be sailing towards a straightforward triumph in the showdown between the French league winners and the French Cup holders after the French winger opened the scoring in the opening stages.
Yet, Marseille struck twice in the closing moments to seize a surprise advantage. Initially, Mason Greenwood converted from the spot-kick, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a remarkable turn of fortune, the Portuguese striker snatched a crucial equaliser in the final moments to send the match into a penalty shootout. PSG goalkeeper Chevalier then stood as the key figure, saving crucial kicks from Matt O'Riley and Traore.
In the shootout, Ramos, the midfielder, the full-back, and the young talent all scored with composure for PSG to complete a 4-1 penalty victory.
Now 14-time winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a league and cup double, have now lifted this trophy for the 12th time in the past 13 seasons.
