The Parisian club has now secured the season-opening trophy on fourteen separate times.
Paris Saint-Germain required a stoppage-time equaliser followed by a perfect spot-kick decider to get past their arch-rivals in the Gulf and capture a fourth straight French Super Cup title.
The European champions appeared to be sailing towards a straightforward win in the showdown between the French league winners and the French Cup winners after Ousmane Dembele opened the scoring early on.
However, the southern French side struck twice late to seize a shock advantage. Initially, Mason Greenwood converted from the spot-kick, before Willian Pacho unfortunately directed the ball into his own net for an own goal.
In a remarkable turn of fortune, the Portuguese striker grabbed a crucial leveler in the final seconds to force the contest into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the hero, stopping crucial attempts from O'Riley and Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored successfully for PSG to seal a 4-1 shootout victory.
The record winners PSG, who met last season's Ligue 1 runners-up Marseille after achieving a domestic double, have now won this trophy for the 12th time in the past 13 seasons.
