The Parisian club has now claimed the season-opening cup on 14 separate occasions.
Paris Saint-Germain required a stoppage-time leveler followed by a perfect penalty shootout to overcome their arch-rivals in the Gulf and capture a record-extending fourth consecutive French Super Cup title.
The Champions League holders appeared to be coasting towards a comfortable triumph in the showdown featuring the Ligue 1 champions and the Coupe de France holders after the French winger found the scoring early on.
However, the southern French side struck two times late to seize a shock advantage. Initially, Mason Greenwood converted from the penalty spot, before the defender unfortunately turned the ball into his own net for an own goal.
In a breathtaking twist of events, the Portuguese striker snatched a vital leveler in the dying seconds to force the match into a deciding shootout. PSG goalkeeper Chevalier then stood as the key figure, stopping crucial attempts from Matt O'Riley and Traore.
In the shootout, Ramos, the midfielder, Nuno Mendes, and Desire Doue all scored successfully for PSG to complete 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 league and cup double, have now lifted this trophy for the twelfth time in the last thirteen seasons.
