The Parisian club has now won the season-opening trophy on 14 separate occasions.
Paris Saint-Germain required a stoppage-time equaliser followed by a successful spot-kick decider to get past Marseille in the Gulf and secure a fourth straight French Super Cup victory.
The European champions appeared to be sailing towards a comfortable win in the showdown between the French league champions and the Coupe de France winners after the French winger opened the scoring early on.
However, the southern French side struck two times late to take a shock advantage. Initially, Mason Greenwood scored from the penalty spot, before the defender inadvertently directed the ball into his own net for an own-goal.
In a remarkable turn of events, Goncalo Ramos grabbed a vital equaliser in the final moments to send the match into a deciding shootout. PSG goalkeeper Chevalier then stood as the key figure, saving decisive kicks from Matt O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted successfully for Paris Saint-Germain to complete a convincing penalty victory.
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 lifted this competition for the twelfth time in the last thirteen seasons.
