The Parisian club has now claimed the prestigious trophy on 14 separate occasions.
The Parisian giants required a stoppage-time leveler followed by a successful penalty shootout to overcome Marseille in Kuwait and secure a fourth straight French Super Cup title.
The European champions appeared to be sailing towards a comfortable triumph in the showdown between the Ligue 1 champions and the Coupe de France winners after Ousmane Dembele found the net in the opening stages.
Yet, Marseille struck twice late to take a surprise lead. First, Mason Greenwood converted from the spot-kick, before the defender unfortunately directed the ball into his own net for an own-goal.
In a breathtaking twist of fortune, Goncalo Ramos grabbed a vital leveler in the dying moments to force the match into a deciding shootout. PSG goalkeeper Chevalier then stood as the hero, stopping crucial attempts from O'Riley and Traore.
In the shootout, Ramos, Vitinha, the full-back, and the young talent all scored with composure for PSG to complete a 4-1 penalty victory.
Now 14-time winners Paris Saint-Germain, who met last season's Ligue 1 runners-up Marseille after completing a domestic double, have now lifted this competition for the twelfth time in the past 13 seasons.
