The Parisian club has now secured the season-opening trophy on fourteen separate occasions.
Paris Saint-Germain needed a dramatic leveler followed by a successful penalty shootout to overcome Marseille in Kuwait and secure a fourth straight French Super Cup title.
The European champions seemed to be sailing towards a comfortable win in the match between the French league champions and the French Cup holders after the French winger opened the net in the opening stages.
However, the southern French side fired twice late to seize a shock lead. Initially, Mason Greenwood scored from the penalty spot, before the defender unfortunately directed the ball into his own net for an own goal.
In a breathtaking turn of fortune, Goncalo Ramos grabbed a crucial equaliser in the final moments to force the match into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the hero, stopping crucial attempts from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all converted successfully for PSG to complete a convincing shootout victory.
The record winners Paris Saint-Germain, who met last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now lifted this trophy for the twelfth time in the past thirteen seasons.
