The Parisian club has now won the prestigious trophy on 14 different occasions.
Paris Saint-Germain needed a dramatic leveler followed by a perfect spot-kick decider to overcome Marseille in the Gulf and secure a fourth straight French Super Cup victory.
The Champions League holders seemed to be sailing towards a comfortable win in the showdown between the Ligue 1 champions and the Coupe de France holders after the French winger opened the net in the opening stages.
However, Marseille fired twice late to seize a surprise lead. First, Mason Greenwood scored from the penalty spot, before the defender unfortunately turned the ball into his own net for an own-goal.
In a breathtaking twist of fortune, Goncalo Ramos snatched a vital leveler in the final seconds to force the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the hero, saving decisive attempts from O'Riley and Traore.
From the spot, Ramos, Vitinha, the full-back, and Desire Doue all scored successfully for Paris Saint-Germain to complete a convincing penalty win.
Now 14-time winners PSG, who met last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now lifted this trophy for the twelfth time in the last 13 seasons.
