PSG has now won the prestigious trophy on 14 separate times.
The Parisian giants needed a dramatic leveler followed by a perfect spot-kick decider to overcome their arch-rivals in the Gulf and capture a record-extending fourth consecutive French Super Cup title.
The European champions seemed to be coasting towards a straightforward win in the showdown featuring the French league champions and the Coupe de France holders after Ousmane Dembele found the scoring in the opening stages.
However, the southern French side fired two times in the closing moments to seize a shock advantage. 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 breathtaking twist of fortune, the Portuguese striker grabbed a vital leveler in the final seconds to force the contest into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the key figure, saving decisive attempts from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and the young talent all converted with composure for Paris Saint-Germain to seal a 4-1 shootout victory.
Now 14-time winners Paris Saint-Germain, who met last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now won this trophy for the 12th time in the past thirteen years.
