The Parisian club has now secured the season-opening trophy on fourteen different times.
Paris Saint-Germain needed a dramatic leveler followed by a perfect penalty shootout to overcome their arch-rivals in the Gulf and secure a fourth straight French Super Cup title.
The Champions League holders appeared to be sailing towards a straightforward win in the match between the French league champions and the Coupe de France winners after Ousmane Dembele found the net in the opening stages.
However, the southern French side struck twice late to take a surprise lead. First, Mason Greenwood converted from the spot-kick, before the defender inadvertently turned the ball into his own net for an own-goal.
In a breathtaking twist of fortune, the Portuguese striker grabbed a vital leveler in the dying seconds to force the match into a penalty shootout. PSG goalkeeper Chevalier then stood as the key figure, saving crucial kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and the young talent all converted with composure for PSG to seal a convincing penalty win.
Now 14-time champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after achieving a domestic double, have now lifted this competition for the 12th time in the past thirteen years.
