PSG has now claimed the prestigious trophy on 14 different times.
Paris Saint-Germain needed a stoppage-time equaliser followed by a successful penalty shootout to overcome Marseille in the Gulf and secure a record-extending fourth consecutive French Super Cup victory.
The European champions appeared to be coasting towards a straightforward triumph in the match featuring the French league winners and the Coupe de France winners after Ousmane Dembele opened the net early on.
However, the southern French side fired twice late to take a shock lead. First, Mason Greenwood converted from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a remarkable twist of events, the Portuguese striker snatched a vital equaliser in the dying moments to force the match into a penalty shootout. PSG goalkeeper Chevalier then stood as the hero, stopping crucial attempts from O'Riley and Traore.
From the spot, Ramos, Vitinha, the full-back, and Desire Doue all converted with composure for Paris Saint-Germain to complete a convincing shootout win.
The record champions Paris Saint-Germain, who met last season's Ligue 1 runners-up Marseille after achieving a domestic double, have now lifted this trophy for the twelfth time in the last thirteen seasons.
