The Parisian club has now won the prestigious trophy on 14 separate occasions.
The Parisian giants required a dramatic equaliser followed by a perfect penalty shootout to overcome their arch-rivals in Kuwait and capture a fourth straight French Super Cup victory.
The European champions appeared to be sailing towards a comfortable triumph in the showdown featuring the French league winners and the Coupe de France holders after Ousmane Dembele found the scoring early on.
Yet, Marseille struck two times in the closing moments to take a shock lead. First, Mason Greenwood converted from the penalty spot, before Willian Pacho inadvertently directed the ball into his own net for an own-goal.
In a remarkable twist of events, the Portuguese striker grabbed a crucial equaliser in the final moments to force the match into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then stood as the hero, stopping decisive kicks from O'Riley and Traore.
From the spot, Ramos, Vitinha, the full-back, and the young talent all scored with composure for PSG to complete a 4-1 shootout win.
Now 14-time winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now won this competition for the twelfth time in the past thirteen seasons.
