PSG has now secured the season-opening cup on 14 separate times.
The Parisian giants required a stoppage-time leveler followed by a perfect spot-kick decider to get past Marseille in the Gulf and capture a fourth straight French Super Cup victory.
The Champions League holders seemed to be sailing towards a comfortable triumph in the showdown featuring the French league champions and the French Cup winners after Ousmane Dembele found the scoring in the opening stages.
Yet, Marseille struck twice in the closing moments to seize a surprise lead. Initially, the English forward converted from the penalty spot, before Willian Pacho inadvertently directed the ball into his own net for an own-goal.
In a breathtaking twist of fortune, Goncalo Ramos snatched a crucial leveler in the final moments to send the contest into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the key figure, saving decisive attempts from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and the young talent all converted successfully for Paris Saint-Germain to complete a 4-1 penalty victory.
Now 14-time winners Paris Saint-Germain, who met last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now lifted this trophy for the 12th time in the past thirteen years.
