The Parisian club has now won the season-opening trophy on 14 different occasions.
Paris Saint-Germain required a dramatic leveler followed by a successful penalty shootout to overcome their arch-rivals in the Gulf and secure a fourth straight French Super Cup victory.
The European champions seemed to be coasting towards a straightforward triumph in the match featuring the French league winners and the Coupe de France holders after the French winger opened the scoring in the opening stages.
However, the southern French side fired twice 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 fortune, the Portuguese striker snatched a crucial equaliser in the final seconds to force the match into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, stopping decisive kicks from Matt O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all scored with composure for PSG to complete a 4-1 shootout win.
Now 14-time champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now lifted this trophy for the twelfth time in the past 13 years.
