The Parisian club has now claimed the prestigious cup on 14 different times.
The Parisian giants needed a stoppage-time leveler followed by a perfect penalty shootout to get past their arch-rivals in the Gulf and capture a record-extending fourth consecutive French Super Cup victory.
The European champions appeared to be coasting towards a comfortable win in the match featuring the Ligue 1 winners and the Coupe de France holders after Ousmane Dembele opened the net in the opening stages.
Yet, the southern French side struck twice in the closing moments to seize a shock advantage. Initially, Mason Greenwood converted from the spot-kick, before Willian Pacho unfortunately directed the ball into his own net for an own goal.
In a remarkable twist of fortune, the Portuguese striker grabbed a crucial equaliser in the dying seconds to send the contest into a penalty shootout. PSG goalkeeper Lucas Chevalier then emerged as the key figure, stopping decisive kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, the full-back, and the young talent all converted successfully for PSG to complete a convincing penalty victory.
Now 14-time winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after achieving a domestic double, have now won this trophy for the 12th time in the last 13 seasons.