The Parisian club has now secured the prestigious cup on 14 different occasions.
The Parisian giants needed a stoppage-time leveler followed by a perfect penalty shootout to overcome Marseille in Kuwait and secure a record-extending fourth consecutive French Super Cup victory.
The Champions League holders seemed to be coasting towards a straightforward win in the match between the French league winners and the Coupe de France winners after Ousmane Dembele opened the net early on.
Yet, the southern French side struck twice in the closing moments to seize a shock lead. Initially, Mason Greenwood scored from the spot-kick, before the defender unfortunately turned the ball into his own net for an own-goal.
In a remarkable twist of events, Goncalo Ramos snatched a vital leveler in the final moments to force the contest 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, Goncalo Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored with composure for PSG to seal a convincing penalty victory.
The record champions PSG, who faced last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now won this competition for the twelfth time in the last thirteen seasons.