PSG has now won the prestigious trophy on 14 separate times.
The Parisian giants required a dramatic leveler followed by a perfect spot-kick decider to get past Marseille in the Gulf and secure a record-extending fourth consecutive French Super Cup victory.
The European champions appeared to be sailing towards a straightforward triumph in the match between the Ligue 1 champions and the Coupe de France winners after the French winger opened the scoring early on.
Yet, the southern French side fired twice late to take a shock advantage. Initially, Mason Greenwood converted from the spot-kick, before the defender unfortunately directed the ball into his own net for an own goal.
In a breathtaking twist of fortune, Goncalo Ramos snatched a crucial leveler in the final seconds to force the match into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the hero, stopping decisive kicks from O'Riley and Traore.
In the shootout, Goncalo Ramos, Vitinha, the full-back, and the young talent all scored with composure for PSG to seal a convincing penalty win.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a league and cup double, have now won this trophy for the 12th time in the past 13 seasons.
