The Parisian club has now secured the prestigious trophy on 14 separate occasions.
Paris Saint-Germain required a dramatic equaliser followed by a successful penalty shootout to overcome their arch-rivals in the Gulf and secure a record-extending fourth consecutive French Super Cup title.
The Champions League holders seemed to be sailing towards a straightforward triumph in the match featuring the French league winners and the French Cup winners after Ousmane Dembele found the net early on.
Yet, Marseille struck twice in the closing moments to take a shock lead. Initially, the English forward converted from the spot-kick, before the defender unfortunately directed the ball into his own net for an own goal.
In a breathtaking twist of fortune, Goncalo Ramos snatched a crucial equaliser in the dying moments to send the contest into a deciding shootout. PSG goalkeeper Lucas Chevalier then stood as the hero, stopping decisive attempts from O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, the full-back, and the young talent all scored successfully for Paris Saint-Germain to seal a convincing penalty win.
The record champions PSG, who faced last season's Ligue 1 second-placed team Olympique de Marseille after achieving a domestic double, have now lifted this trophy for the twelfth time in the past thirteen seasons.
