The Parisian club has now claimed the season-opening trophy on 14 separate times.
Paris Saint-Germain needed 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 Champions League holders seemed to be coasting towards a straightforward win in the showdown between the French league winners and the French Cup holders after Ousmane Dembele opened the net in the opening stages.
Yet, the southern French side fired twice late to seize a shock advantage. First, the English forward scored from the penalty spot, before the defender inadvertently directed the ball into his own net for an own-goal.
In a remarkable twist of events, the Portuguese striker grabbed a crucial leveler in the dying moments to send the match into a penalty shootout. PSG goalkeeper Chevalier then emerged as the key figure, saving crucial attempts from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all scored successfully for PSG to seal a 4-1 penalty victory.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now won this trophy for the 12th time in the past 13 years.
