PSG has now claimed the prestigious trophy on 14 separate occasions.
The Parisian giants needed a stoppage-time leveler followed by a perfect penalty shootout to get past Marseille in Kuwait and capture a fourth straight French Super Cup victory.
The Champions League holders appeared to be coasting towards a comfortable triumph in the match between the French league champions and the French Cup holders after Ousmane Dembele found the scoring in the opening stages.
Yet, Marseille fired two times late to take a shock advantage. Initially, the English forward converted from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own goal.
In a remarkable turn of fortune, the Portuguese striker snatched a crucial equaliser in the final seconds to force the match into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the key figure, saving decisive kicks from O'Riley and Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted successfully for Paris Saint-Germain to seal a 4-1 penalty win.
Now 14-time winners PSG, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now won this competition for the twelfth time in the last 13 seasons.
