The Parisian club has now claimed the prestigious cup on 14 different times.
Paris Saint-Germain required a stoppage-time leveler followed by a successful penalty shootout to overcome their arch-rivals in the Gulf and capture a fourth straight French Super Cup victory.
The Champions League holders appeared to be coasting towards a straightforward triumph in the match between the Ligue 1 winners and the French Cup winners after the French winger opened the scoring in the opening stages.
Yet, the southern French side struck two times in the closing moments to seize a shock lead. Initially, the English forward converted from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a breathtaking turn of events, Goncalo Ramos grabbed a vital equaliser in the final seconds to send the contest into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, saving crucial attempts from O'Riley and Traore.
In the shootout, Ramos, the midfielder, Nuno Mendes, and Desire Doue all scored successfully for PSG to seal a 4-1 shootout victory.
The record champions Paris Saint-Germain, who met last season's Ligue 1 runners-up Marseille after achieving a league and cup double, have now lifted this competition for the twelfth time in the past thirteen seasons.
