PSG has now claimed the prestigious trophy on fourteen separate occasions.
The Parisian giants needed a stoppage-time leveler followed by a perfect penalty shootout to overcome their arch-rivals in the Gulf and secure a fourth straight French Super Cup victory.
The Champions League holders seemed to be sailing towards a straightforward win in the showdown between the French league winners and the Coupe de France winners after Ousmane Dembele found the net in the opening stages.
However, the southern French side struck twice in the closing moments to take a surprise lead. Initially, Mason Greenwood 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 fortune, the Portuguese striker grabbed a crucial equaliser in the dying seconds to send the contest into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the hero, saving crucial attempts from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all scored successfully for Paris Saint-Germain to complete a 4-1 penalty win.
Now 14-time champions PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now lifted this trophy for the twelfth time in the past thirteen years.
