The Parisian club has now secured the prestigious trophy on fourteen separate times.
The Parisian giants needed a stoppage-time equaliser followed by a successful spot-kick decider to get past their arch-rivals in the Gulf and capture a record-extending fourth consecutive French Super Cup title.
The European champions appeared to be sailing towards a straightforward triumph in the showdown featuring the French league winners and the Coupe de France winners after Ousmane Dembele opened the scoring early on.
Yet, Marseille struck twice late to seize a shock lead. First, the English forward converted from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own-goal.
In a breathtaking turn of fortune, Goncalo Ramos snatched a crucial equaliser in the final seconds to force the contest into a deciding shootout. PSG goalkeeper Chevalier then emerged as the hero, stopping crucial attempts from O'Riley and Traore.
From the spot, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all scored 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 competition for the 12th time in the last 13 seasons.
