The Parisian club has now claimed the season-opening cup on fourteen separate times.
Paris Saint-Germain required a stoppage-time leveler followed by a successful spot-kick decider to overcome their arch-rivals in Kuwait and secure a fourth straight French Super Cup victory.
The European champions seemed to be sailing towards a straightforward triumph in the match between the Ligue 1 champions and the French Cup holders after Ousmane Dembele found the net early on.
However, Marseille struck two times late to take a surprise advantage. First, Mason Greenwood scored from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a breathtaking twist of fortune, Goncalo Ramos snatched a crucial leveler in the final seconds to send the contest into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the hero, stopping crucial kicks from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, Nuno Mendes, and Desire Doue all converted successfully for PSG to seal a convincing penalty victory.
Now 14-time winners PSG, who met last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now won this trophy for the 12th time in the last 13 seasons.
