The Parisian club has now won the prestigious trophy on 14 different occasions.
Paris Saint-Germain needed a stoppage-time leveler followed by a successful penalty shootout to get past Marseille in the Gulf and capture a fourth straight French Super Cup title.
The European champions appeared to be coasting towards a comfortable triumph in the showdown featuring the Ligue 1 winners and the French Cup holders after Ousmane Dembele found the net early on.
However, Marseille fired two times in the closing moments to take a surprise advantage. First, Mason Greenwood scored from the spot-kick, before the defender unfortunately directed the ball into his own net for an own goal.
In a breathtaking turn of fortune, the Portuguese striker snatched a crucial leveler in the dying moments to send the contest into a penalty shootout. PSG goalkeeper Lucas Chevalier then stood as the hero, saving decisive attempts from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted with composure for Paris Saint-Germain to seal a 4-1 shootout victory.
The record winners PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after completing a league and cup double, have now won this competition for the 12th time in the past thirteen years.
