PSG has now claimed the season-opening cup on fourteen separate occasions.
The Parisian giants needed a dramatic 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 European champions seemed to be sailing towards a straightforward win in the showdown between the French league champions and the Coupe de France winners after the French winger found the scoring early on.
Yet, the southern French side struck two times late to take a shock lead. Initially, Mason Greenwood scored from the spot-kick, before the defender inadvertently directed the ball into his own net for an own-goal.
In a breathtaking turn of fortune, the Portuguese striker snatched a crucial leveler in the dying seconds to send the contest into a deciding shootout. PSG goalkeeper Chevalier then stood as the hero, saving decisive kicks from Matt O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, the full-back, and Desire Doue all scored successfully for PSG to complete a 4-1 penalty win.
The record winners Paris Saint-Germain, who met last season's Ligue 1 runners-up Marseille after achieving a league and cup double, have now lifted this trophy for the 12th time in the last 13 seasons.
