The Parisian club has now claimed the prestigious trophy on 14 separate occasions.
The Parisian giants needed a dramatic leveler followed by a successful penalty shootout to get past Marseille in Kuwait and secure a fourth straight French Super Cup victory.
The European champions appeared to be coasting towards a straightforward win in the match featuring the French league winners and the French Cup winners after the French winger found the net in the opening stages.
However, Marseille fired twice in the closing moments to seize a shock advantage. Initially, 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 breathtaking twist of events, Goncalo Ramos snatched a vital equaliser in the final seconds to send the contest into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the hero, stopping crucial kicks from O'Riley and Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and the young talent all converted with composure for PSG to complete a 4-1 shootout victory.
Now 14-time winners Paris Saint-Germain, who met last season's Ligue 1 runners-up Marseille after achieving a domestic double, have now lifted this competition for the twelfth time in the past thirteen seasons.