The Parisian club has now won the season-opening cup on 14 separate times.
Paris Saint-Germain needed a stoppage-time leveler followed by a successful spot-kick decider to get past 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 match between the French league winners and the Coupe de France holders after the French winger opened the scoring early on.
Yet, Marseille fired twice late to seize a surprise lead. First, Mason Greenwood scored from the spot-kick, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a breathtaking turn of events, the Portuguese striker snatched a vital equaliser in the final moments to force the match into a deciding shootout. PSG goalkeeper Chevalier then emerged as the hero, saving decisive attempts from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and the young talent all converted successfully for Paris Saint-Germain to complete a convincing shootout win.
Now 14-time winners Paris Saint-Germain, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now won this trophy for the twelfth time in the past thirteen years.
