The Parisian club has now won the prestigious trophy on fourteen different times.
Paris Saint-Germain required a dramatic leveler followed by a successful penalty shootout to get past Marseille in the Gulf and capture a record-extending fourth consecutive French Super Cup victory.
The Champions League holders appeared to be coasting towards a comfortable win in the showdown featuring the French league winners and the French Cup holders after Ousmane Dembele found the scoring in the opening stages.
Yet, the southern French side struck twice late to take a surprise advantage. Initially, Mason Greenwood scored from the penalty spot, before the defender inadvertently directed the ball into his own net for an own-goal.
In a breathtaking twist of fortune, Goncalo Ramos grabbed a crucial leveler in the dying seconds to force the match into a deciding shootout. PSG goalkeeper Lucas Chevalier then emerged as the key figure, stopping decisive attempts from O'Riley and Traore.
From the spot, Ramos, the midfielder, Nuno Mendes, and the young talent all converted with composure for PSG to seal a convincing penalty win.
Now 14-time winners PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after completing a domestic double, have now won this competition for the 12th time in the last thirteen years.