The Parisian club has now secured the season-opening cup on 14 different times.
Paris Saint-Germain required a stoppage-time leveler followed by a perfect penalty shootout to get past Marseille in the Gulf and secure a fourth straight French Super Cup victory.
The Champions League holders seemed to be sailing towards a straightforward win in the showdown between the French league winners and the Coupe de France holders after Ousmane Dembele found the net early on.
However, Marseille fired twice in the closing moments to take a surprise lead. Initially, Mason Greenwood converted from the penalty spot, before Willian Pacho inadvertently directed the ball into his own net for an own goal.
In a remarkable turn of fortune, Goncalo Ramos grabbed a crucial equaliser in the final moments to force the contest into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the hero, saving crucial kicks from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all scored successfully for PSG to complete a 4-1 penalty win.
Now 14-time winners Paris Saint-Germain, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a league and cup double, have now won this competition for the 12th time in the last 13 seasons.
