The Parisian club has now won the season-opening cup on fourteen separate occasions.
Paris Saint-Germain needed a stoppage-time equaliser followed by a perfect penalty shootout to get past their arch-rivals in the Gulf and secure a fourth straight French Super Cup title.
The Champions League holders seemed to be sailing towards a straightforward win in the showdown featuring the Ligue 1 champions and the French Cup winners after Ousmane Dembele opened the net early on.
However, Marseille fired twice late to seize a surprise lead. Initially, the English forward scored from the penalty spot, before the defender unfortunately directed the ball into his own net for an own goal.
In a breathtaking turn of events, the Portuguese striker snatched a crucial leveler in the final moments to send the contest into a deciding shootout. PSG goalkeeper Chevalier then emerged as the hero, stopping crucial attempts from Matt O'Riley and Traore.
From the spot, Ramos, Vitinha, the full-back, and the young talent all scored with composure for PSG to seal a 4-1 shootout win.
The record champions PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a domestic double, have now won this trophy for the twelfth time in the last thirteen seasons.
