The Parisian club has now secured the season-opening trophy on 14 different times.
The Parisian giants needed a stoppage-time equaliser followed by a successful penalty shootout to overcome their arch-rivals in the Gulf and secure a record-extending fourth consecutive French Super Cup title.
The European champions appeared to be coasting towards a comfortable win in the match between the French league champions and the Coupe de France holders after Ousmane Dembele opened the net in the opening stages.
However, the southern French side fired two times late to seize a shock advantage. First, the English forward converted from the penalty spot, before the defender unfortunately directed the ball into his own net for an own-goal.
In a breathtaking turn of events, Goncalo Ramos grabbed a crucial equaliser in the dying seconds to send the match into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the hero, stopping decisive attempts from Matt O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored with composure for PSG to seal a convincing penalty win.
Now 14-time winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a league and cup double, have now lifted this trophy for the 12th time in the past 13 years.
