PSG has now won the season-opening cup on fourteen separate occasions.
Paris Saint-Germain needed a stoppage-time equaliser 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 European champions appeared to be sailing towards a straightforward win in the match between the French league champions and the Coupe de France winners after Ousmane Dembele found the net early on.
Yet, the southern French side fired twice late to take a shock advantage. Initially, the English forward scored from the penalty spot, before the defender inadvertently directed the ball into his own net for an own goal.
In a remarkable turn of events, the Portuguese striker snatched a vital equaliser in the dying seconds to send the contest into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the hero, stopping decisive attempts from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, the full-back, and the young talent all converted successfully for Paris Saint-Germain to seal a 4-1 penalty victory.
Now 14-time winners PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a league and cup double, have now won this trophy for the 12th time in the last thirteen seasons.
