The Parisian club has now claimed the season-opening cup on 14 separate occasions.
The Parisian giants required a dramatic leveler followed by a perfect penalty shootout to get past their arch-rivals in the Gulf and capture a record-extending fourth consecutive French Super Cup victory.
The Champions League holders appeared to be sailing towards a straightforward triumph in the showdown between the French league champions and the Coupe de France holders after the French winger found the net in the opening stages.
Yet, the southern French side struck twice late to seize a shock lead. Initially, Mason Greenwood converted from the spot-kick, before the defender unfortunately directed the ball into his own net for an own goal.
In a breathtaking turn of fortune, the Portuguese striker snatched a vital leveler in the dying moments to force the contest into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the hero, saving decisive attempts from Matt O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, the full-back, and Desire Doue all converted successfully for Paris Saint-Germain to seal a convincing penalty victory.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now lifted this competition for the twelfth time in the last thirteen seasons.