PSG has now secured the season-opening trophy on fourteen different occasions.
The Parisian giants needed a stoppage-time equaliser followed by a perfect penalty shootout to get past Marseille in the Gulf and secure a fourth straight French Super Cup title.
The Champions League holders seemed to be sailing towards a straightforward win in the match featuring the French league champions and the Coupe de France winners after the French winger opened the net early on.
Yet, Marseille struck twice late to take a surprise lead. Initially, Mason Greenwood converted from the penalty spot, before the defender unfortunately turned the ball into his own net for an own goal.
In a remarkable turn of events, the Portuguese striker snatched a crucial equaliser in the final moments to send the contest into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the key figure, saving crucial attempts from O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, the full-back, and the young talent all converted successfully for PSG to complete a convincing shootout win.
Now 14-time champions PSG, who faced last season's Ligue 1 runners-up Marseille after achieving a domestic double, have now won this trophy for the 12th time in the past 13 years.