PSG has now claimed the season-opening cup on 14 different times.
The Parisian giants required a dramatic leveler followed by a successful spot-kick decider to get past Marseille in the Gulf and secure a fourth straight French Super Cup victory.
The European champions appeared to be coasting towards a straightforward triumph in the match featuring the French league champions and the French Cup holders after Ousmane Dembele opened the scoring early on.
However, the southern French side struck twice in the closing moments to take a surprise lead. First, 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, the Portuguese striker snatched a crucial leveler in the final moments to send the contest into a penalty shootout. PSG goalkeeper Lucas Chevalier then stood as the key figure, stopping decisive attempts from O'Riley and Traore.
In the shootout, Goncalo Ramos, the midfielder, the full-back, and the young talent all converted with composure for Paris Saint-Germain to seal 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 domestic double, have now won this competition for the twelfth time in the last thirteen seasons.
