The Parisian club has now secured the season-opening trophy on fourteen separate occasions.
The Parisian giants needed a stoppage-time leveler followed by a successful spot-kick decider to overcome Marseille in the Gulf and secure a fourth straight French Super Cup title.
The Champions League holders seemed to be coasting towards a comfortable triumph in the showdown between the Ligue 1 winners and the French Cup winners after Ousmane Dembele opened the net early on.
However, Marseille struck twice in the closing moments to take a shock lead. First, Mason Greenwood scored from the spot-kick, before Willian Pacho unfortunately directed the ball into his own net for an own goal.
In a breathtaking turn of fortune, the Portuguese striker grabbed a vital leveler in the final moments to force the match into a penalty shootout. PSG goalkeeper Chevalier then stood as the hero, saving crucial attempts from O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, Nuno Mendes, and the young talent all converted successfully for PSG to complete a convincing penalty victory.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 runners-up Olympique de Marseille after completing a league and cup double, have now lifted this trophy for the twelfth time in the last thirteen years.
