PSG has now claimed the season-opening cup on 14 different occasions.
Paris Saint-Germain required a stoppage-time leveler followed by a successful penalty shootout to overcome 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 straightforward triumph in the showdown between the French league winners and the Coupe de France winners after Ousmane Dembele found the net early on.
Yet, the southern French side struck two times late to take a shock lead. First, the English forward scored from the spot-kick, before the defender unfortunately directed the ball into his own net for an own-goal.
In a remarkable turn of fortune, the Portuguese striker grabbed a crucial leveler in the final seconds to force the contest into a deciding shootout. PSG goalkeeper Lucas Chevalier then emerged as the hero, saving crucial kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and the young talent all converted successfully for PSG to complete a convincing penalty victory.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now won this competition for the twelfth time in the last thirteen years.
