PSG has now secured the prestigious cup on fourteen separate times.
The Parisian giants needed a stoppage-time equaliser followed by a successful spot-kick decider to overcome Marseille in the Gulf and secure a fourth straight French Super Cup victory.
The European champions seemed to be sailing towards a comfortable win in the match featuring the French league champions and the French Cup winners after Ousmane Dembele opened the scoring early on.
Yet, Marseille fired two times in the closing moments to take a surprise lead. First, Mason Greenwood converted from the spot-kick, before the defender unfortunately turned the ball into his own net for an own goal.
In a breathtaking turn of fortune, Goncalo Ramos snatched a crucial equaliser in the dying moments to force the match into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then stood as the key figure, saving decisive kicks from Matt O'Riley and Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted 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 Marseille after achieving a domestic double, have now lifted this competition for the twelfth time in the last 13 years.