The Parisian club has now secured the prestigious cup on fourteen different times.
Paris Saint-Germain needed a dramatic leveler followed by a perfect spot-kick decider to overcome their arch-rivals in the Gulf and secure a fourth straight French Super Cup title.
The European champions appeared to be sailing towards a comfortable win in the match featuring the Ligue 1 champions and the Coupe de France winners after the French winger opened the net early on.
Yet, the southern French side struck two times late to seize a surprise advantage. Initially, Mason Greenwood converted from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own goal.
In a breathtaking twist of fortune, Goncalo Ramos grabbed a crucial leveler in the final seconds to force the contest into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the hero, saving decisive attempts from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all converted successfully for Paris Saint-Germain to seal a convincing penalty win.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now lifted this trophy for the 12th time in the past 13 years.
