The Parisian club has now secured the prestigious trophy on 14 separate times.
The Parisian giants required 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 victory.
The Champions League holders seemed to be sailing towards a straightforward win in the showdown featuring the Ligue 1 winners and the French Cup winners after the French winger opened the scoring early on.
Yet, the southern French side struck two times late to seize a surprise lead. First, Mason Greenwood scored from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a breathtaking turn of fortune, Goncalo Ramos grabbed a vital leveler in the dying seconds to force the contest into a deciding shootout. PSG goalkeeper Chevalier then emerged as the key figure, saving crucial attempts from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all converted successfully for Paris Saint-Germain to seal a 4-1 penalty win.
Now 14-time champions PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now won this trophy for the twelfth time in the past 13 seasons.
