The Parisian club has now claimed the season-opening trophy on fourteen separate occasions.
Paris Saint-Germain required a stoppage-time equaliser followed by a successful penalty shootout to overcome their arch-rivals in the Gulf and secure a fourth straight French Super Cup title.
The Champions League holders appeared to be sailing towards a comfortable triumph in the showdown between the Ligue 1 champions and the French Cup holders after the French winger found the net early on.
However, Marseille struck twice in the closing moments to take a shock lead. Initially, Mason Greenwood scored from the penalty spot, before Willian Pacho unfortunately turned the ball into his own net for an own-goal.
In a breathtaking turn of fortune, the Portuguese striker snatched a vital leveler in the final seconds to force the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the hero, saving decisive kicks from Matt O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, the full-back, and Desire Doue all scored successfully for PSG to seal a 4-1 shootout win.
Now 14-time champions PSG, who faced last season's Ligue 1 runners-up Marseille after completing a domestic double, have now won this competition for the 12th time in the last thirteen years.
