The Parisian club has now claimed the season-opening trophy on 14 separate occasions.
Paris Saint-Germain required a stoppage-time leveler followed by a successful penalty shootout to get past Marseille in the Gulf and capture a fourth straight French Super Cup victory.
The Champions League holders seemed to be sailing towards a straightforward win in the match between the French league winners and the Coupe de France holders after Ousmane Dembele found the scoring in the opening stages.
However, Marseille struck two times in the closing moments to take a shock lead. First, Mason Greenwood scored from the penalty spot, before the defender unfortunately directed the ball into his own net for an own goal.
In a remarkable twist of events, Goncalo Ramos grabbed a vital equaliser in the final seconds to send the contest into a deciding shootout. PSG goalkeeper Chevalier then stood as the hero, stopping decisive kicks from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted successfully for Paris Saint-Germain to seal a convincing penalty win.
Now 14-time champions PSG, who faced last season's Ligue 1 runners-up Marseille after achieving a league and cup double, have now won this trophy for the twelfth time in the past 13 years.
