The Parisian club has now claimed the prestigious trophy on 14 separate times.
The Parisian giants required a stoppage-time equaliser followed by a successful spot-kick decider to overcome their arch-rivals in the Gulf and capture a fourth straight French Super Cup victory.
The European champions appeared to be sailing towards a straightforward win in the match between the Ligue 1 champions and the French Cup holders after Ousmane Dembele opened the scoring in the opening stages.
Yet, Marseille fired two times late to seize a surprise lead. Initially, Mason Greenwood converted from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own-goal.
In a remarkable twist of fortune, the Portuguese striker grabbed a crucial leveler in the final seconds to send the contest into a deciding shootout. PSG goalkeeper Lucas Chevalier then emerged as the hero, stopping crucial kicks from O'Riley and Traore.
In the shootout, Ramos, the midfielder, Nuno Mendes, and Desire Doue all converted with composure for PSG to complete a convincing penalty win.
The record 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 12th time in the last 13 seasons.
