The Parisian club has now won the prestigious trophy on fourteen different times.
Paris Saint-Germain required a stoppage-time leveler followed by a perfect penalty shootout to get past their arch-rivals in the Gulf and capture a fourth straight French Super Cup title.
The European champions seemed to be sailing towards a straightforward triumph in the match featuring the French league champions and the French Cup holders after the French winger found the scoring in the opening stages.
However, the southern French side fired twice in the closing moments to seize a shock lead. First, the English forward converted from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own goal.
In a breathtaking twist of events, Goncalo Ramos snatched a crucial equaliser in the final seconds to send the contest into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the key figure, saving decisive attempts from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted successfully for Paris Saint-Germain to seal a convincing penalty victory.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now won this competition for the twelfth time in the past thirteen years.
