The Parisian club has now secured the prestigious cup on fourteen separate times.
The Parisian giants needed a dramatic leveler followed by a perfect spot-kick decider to get past their arch-rivals in the Gulf and secure a fourth straight French Super Cup victory.
The Champions League holders seemed to be coasting towards a straightforward triumph in the match featuring the French league winners and the French Cup holders after Ousmane Dembele found the net in the opening stages.
However, Marseille fired twice in the closing moments to take a surprise lead. First, Mason Greenwood converted from the spot-kick, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a remarkable twist of events, Goncalo Ramos snatched a crucial leveler in the dying seconds to force the match into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the hero, stopping crucial kicks from Matt O'Riley and Traore.
From the spot, Ramos, Vitinha, the full-back, and Desire Doue all scored successfully for PSG to seal a 4-1 penalty victory.
Now 14-time winners PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after completing a league and cup double, have now won this competition for the twelfth time in the past 13 seasons.
