The Parisian club has now claimed the season-opening trophy on 14 separate occasions.
Paris Saint-Germain required a dramatic leveler followed by a successful penalty shootout to get past their arch-rivals in the Gulf and capture a record-extending fourth consecutive French Super Cup victory.
The European champions seemed to be sailing towards a comfortable triumph in the match between the French league champions and the French Cup winners after Ousmane Dembele opened the scoring in the opening stages.
Yet, Marseille fired two times in the closing moments to take a shock lead. Initially, the English forward scored from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a remarkable twist of events, Goncalo Ramos snatched a crucial leveler in the final seconds to send the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the key figure, saving decisive kicks from O'Riley and Traore.
From the spot, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all scored with composure for Paris Saint-Germain to seal a convincing penalty win.
Now 14-time champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now lifted this competition for the 12th time in the last thirteen seasons.
