The Parisian club has now claimed the season-opening cup on 14 different times.
The Parisian giants needed a stoppage-time leveler followed by a perfect spot-kick decider to get past their arch-rivals in Kuwait and secure a fourth straight French Super Cup victory.
The European champions appeared to be coasting towards a straightforward triumph in the match between the French league winners and the Coupe de France holders after Ousmane Dembele found the scoring in the opening stages.
Yet, Marseille fired two times in the closing moments to take a surprise lead. Initially, Mason Greenwood converted from the penalty spot, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a breathtaking twist of events, Goncalo Ramos grabbed a vital leveler in the final moments to force the match into a deciding shootout. PSG goalkeeper Lucas Chevalier then emerged as the key figure, stopping decisive attempts from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and the young talent all scored with composure for Paris Saint-Germain to complete a convincing shootout win.
Now 14-time champions PSG, who faced last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now won this trophy for the 12th time in the last 13 seasons.
