The Parisian club has now won the prestigious cup on fourteen separate times.
The Parisian giants needed a dramatic equaliser followed by a successful spot-kick decider to overcome Marseille in the Gulf and capture a fourth straight French Super Cup victory.
The European champions appeared to be sailing towards a straightforward triumph in the match featuring the Ligue 1 champions and the French Cup winners after Ousmane Dembele found the scoring early on.
Yet, the southern French side struck twice in the closing moments to seize a surprise lead. First, the English forward scored from the penalty spot, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a breathtaking turn of events, the Portuguese striker snatched a crucial equaliser in the final seconds to force the contest into a deciding shootout. PSG goalkeeper Chevalier then stood as the key figure, saving crucial attempts from Matt O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all scored with composure for Paris Saint-Germain to complete a convincing shootout victory.
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 twelfth time in the last thirteen seasons.
