PSG has now won the season-opening cup on 14 separate occasions.
Paris Saint-Germain required a dramatic leveler followed by a successful spot-kick decider to overcome their arch-rivals in the Gulf and capture a fourth straight French Super Cup victory.
The Champions League holders seemed to be coasting towards a comfortable triumph in the showdown between the French league champions and the Coupe de France holders after Ousmane Dembele found the net in the opening stages.
However, the southern French side fired two times late to take a surprise advantage. Initially, Mason Greenwood scored from the spot-kick, before the defender unfortunately turned the ball into his own net for an own-goal.
In a remarkable twist of fortune, Goncalo Ramos snatched a vital leveler in the dying moments to send the match into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the hero, stopping decisive attempts from O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, the full-back, and the young talent all scored successfully for Paris Saint-Germain to seal a 4-1 shootout victory.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 runners-up Olympique de Marseille after completing a domestic double, have now won this trophy for the twelfth time in the last thirteen seasons.
