The Parisian club has now claimed the prestigious cup on fourteen separate times.
The Parisian giants needed a stoppage-time leveler followed by a perfect penalty shootout to get past their arch-rivals in the Gulf and secure a fourth straight French Super Cup victory.
The Champions League holders appeared to be coasting towards a straightforward triumph in the showdown featuring the Ligue 1 winners and the French Cup holders after the French winger opened the scoring early on.
However, the southern French side fired two times late to seize a shock lead. Initially, the English forward converted from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a remarkable twist of fortune, the Portuguese striker snatched a vital leveler in the final moments to force the contest into a deciding shootout. PSG goalkeeper Chevalier then emerged as the hero, saving decisive attempts from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored with composure for PSG to seal a 4-1 shootout victory.
The record champions Paris Saint-Germain, who met last season's Ligue 1 runners-up Marseille after completing a domestic double, have now won this trophy for the 12th time in the past thirteen seasons.
