PSG has now claimed the season-opening trophy on 14 separate times.
The Parisian giants needed a stoppage-time leveler followed by a successful spot-kick decider to get past Marseille in the Gulf and secure a fourth straight French Super Cup title.
The Champions League holders seemed to be coasting towards a comfortable triumph in the match featuring the Ligue 1 champions and the Coupe de France holders after Ousmane Dembele found the scoring early on.
However, the southern French side fired two times late to take a shock advantage. Initially, Mason Greenwood converted from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own goal.
In a breathtaking turn of fortune, Goncalo Ramos grabbed a crucial leveler in the final seconds to send the match into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the key figure, saving crucial attempts from Matt O'Riley and Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored successfully for PSG to seal a 4-1 penalty victory.
The record champions Paris Saint-Germain, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now lifted this trophy for the twelfth time in the past 13 seasons.
