PSG has now secured the season-opening trophy on fourteen separate times.
The Parisian giants required a stoppage-time leveler followed by a perfect penalty shootout to overcome their arch-rivals in the Gulf and capture a fourth straight French Super Cup victory.
The Champions League holders appeared to be sailing towards a comfortable triumph in the showdown between the French league champions and the French Cup holders after Ousmane Dembele opened the scoring in the opening stages.
However, the southern French side struck twice late to take a shock lead. First, the English forward converted from the spot-kick, before the defender unfortunately directed the ball into his own net for an own-goal.
In a remarkable twist of fortune, Goncalo Ramos grabbed a crucial equaliser in the final seconds to force the match into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then stood as the key figure, stopping crucial kicks from O'Riley and Traore.
In the shootout, Ramos, Vitinha, the full-back, and the young talent all scored successfully for Paris Saint-Germain to seal a 4-1 shootout 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 12th time in the past thirteen years.