The Parisian club has now secured the season-opening trophy on 14 different times.
Paris Saint-Germain needed a stoppage-time leveler followed by a successful penalty shootout to get past Marseille in the Gulf and secure a fourth straight French Super Cup title.
The European champions seemed to be coasting towards a straightforward win in the showdown between the French league winners and the French Cup holders after the French winger found the scoring early on.
However, Marseille struck two times late to seize a shock advantage. Initially, Mason Greenwood scored from the spot-kick, before the defender unfortunately directed the ball into his own net for an own-goal.
In a breathtaking turn of events, Goncalo Ramos grabbed a vital equaliser in the final seconds to send the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the hero, saving decisive attempts from O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, Nuno Mendes, and Desire Doue all converted successfully for PSG to seal a convincing penalty win.
Now 14-time winners PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now lifted this competition for the 12th time in the last thirteen seasons.
