PSG has now won the prestigious cup on fourteen different times.
The Parisian giants required a dramatic equaliser followed by a perfect penalty shootout to overcome Marseille in Kuwait and secure a record-extending fourth consecutive French Super Cup title.
The Champions League holders seemed to be sailing towards a comfortable triumph in the showdown between the French league champions and the French Cup holders after Ousmane Dembele found the net in the opening stages.
Yet, Marseille struck two times in the closing moments to seize a surprise advantage. First, Mason Greenwood converted from the spot-kick, before the defender inadvertently directed the ball into his own net for an own-goal.
In a breathtaking turn of fortune, the Portuguese striker grabbed a crucial equaliser in the final seconds to send the contest into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, stopping crucial kicks from O'Riley and Traore.
From the spot, Ramos, the midfielder, the full-back, and the young talent all converted successfully for Paris Saint-Germain to seal a convincing penalty win.
Now 14-time champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Marseille after achieving a domestic double, have now lifted this competition for the twelfth time in the last thirteen years.