The Parisian club has now claimed the prestigious trophy on 14 different times.
Paris Saint-Germain required a dramatic equaliser followed by a successful spot-kick decider to overcome Marseille in the Gulf and secure a fourth straight French Super Cup title.
The European champions seemed to be sailing towards a comfortable win in the showdown featuring the Ligue 1 champions and the Coupe de France holders after Ousmane Dembele opened the scoring in the opening stages.
Yet, the southern French side fired two times late to take a shock advantage. First, the English forward scored from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own goal.
In a breathtaking turn of events, Goncalo Ramos grabbed a vital leveler in the dying moments to send the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the key figure, saving crucial attempts from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored successfully for Paris Saint-Germain to complete a convincing penalty win.
The record winners Paris Saint-Germain, who faced last season's Ligue 1 runners-up Marseille after achieving a domestic double, have now won this competition for the 12th time in the last 13 seasons.
