The Parisian club has now secured the season-opening cup on fourteen separate times.
Paris Saint-Germain needed a stoppage-time equaliser followed by a successful spot-kick decider to overcome Marseille in the Gulf and capture a fourth straight French Super Cup victory.
The Champions League holders seemed to be coasting towards a comfortable win in the showdown featuring the Ligue 1 winners and the Coupe de France holders after Ousmane Dembele found the net early on.
However, Marseille fired two times late to take a shock lead. Initially, the English forward scored from the penalty spot, before the defender unfortunately directed the ball into his own net for an own goal.
In a remarkable turn of fortune, Goncalo Ramos grabbed a crucial leveler in the final seconds to send the match into a deciding shootout. PSG goalkeeper Chevalier then emerged as the hero, saving crucial kicks from Matt O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and Desire Doue all scored with composure for Paris Saint-Germain to seal a convincing shootout victory.
Now 14-time winners PSG, who met last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now won this trophy for the twelfth time in the last 13 seasons.
