PSG has now secured the season-opening cup on 14 separate occasions.
The Parisian giants required a stoppage-time equaliser followed by a successful spot-kick decider to get past their arch-rivals in the Gulf and secure a record-extending fourth consecutive French Super Cup title.
The European champions appeared to be coasting towards a comfortable triumph in the showdown featuring the French league winners and the French Cup holders after Ousmane Dembele found the net early on.
Yet, the southern French side fired two times in the closing moments to take a shock lead. First, the English forward scored 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, Goncalo Ramos grabbed a crucial equaliser in the dying seconds to send the contest into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the hero, saving decisive attempts from O'Riley and Traore.
From the spot, Ramos, Vitinha, the full-back, and the young talent all scored with composure for Paris Saint-Germain to complete a 4-1 penalty win.
The record winners Paris Saint-Germain, who faced last season's Ligue 1 runners-up Marseille after achieving a league and cup double, have now won this competition for the twelfth time in the last thirteen seasons.
