PSG has now claimed the season-opening cup on 14 separate times.
Paris Saint-Germain 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 title.
The European champions appeared to be coasting towards a comfortable win in the showdown between the French league winners and the Coupe de France holders after Ousmane Dembele found the scoring in the opening stages.
However, the southern French side fired two times in the closing moments to take a surprise advantage. Initially, Mason Greenwood scored from the spot-kick, before Willian Pacho unfortunately directed the ball into his own net for an own goal.
In a breathtaking twist of fortune, the Portuguese striker grabbed a vital equaliser in the final moments to force the contest into a penalty shootout. PSG goalkeeper Lucas Chevalier then emerged as the key figure, saving crucial kicks from O'Riley and Traore.
From the spot, Ramos, the midfielder, Nuno Mendes, and Desire Doue all scored with composure for PSG to seal a 4-1 penalty win.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now lifted this trophy for the twelfth time in the past thirteen seasons.
