PSG has now won the prestigious cup on fourteen separate occasions.
The Parisian giants required a dramatic equaliser followed by a perfect penalty shootout to overcome Marseille in the Gulf and capture a record-extending fourth consecutive French Super Cup title.
The Champions League holders appeared to be sailing towards a straightforward win in the match featuring the Ligue 1 winners and the Coupe de France holders after Ousmane Dembele opened the scoring early on.
Yet, the southern French side struck twice late to seize a shock lead. First, the English forward converted from the penalty spot, before the defender inadvertently turned the ball into his own net for an own-goal.
In a remarkable twist of events, Goncalo Ramos grabbed a crucial leveler in the final moments to force the match into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the key figure, stopping crucial attempts from Matt O'Riley and Traore.
In the shootout, Ramos, Vitinha, the full-back, and the young talent all scored with composure for PSG to seal a convincing shootout win.
Now 14-time champions PSG, who met last season's Ligue 1 runners-up Marseille after achieving a domestic double, have now lifted this trophy for the twelfth time in the past thirteen years.