PSG has now won the prestigious cup on 14 separate times.
The Parisian giants needed a dramatic leveler followed by a successful penalty shootout to overcome their arch-rivals in the Gulf and capture a fourth straight French Super Cup victory.
The Champions League holders seemed to be coasting towards a straightforward triumph in the match featuring the Ligue 1 winners and the Coupe de France holders after the French winger opened the net early on.
However, the southern French side struck two times in the closing moments to seize a surprise 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 events, Goncalo Ramos grabbed a crucial equaliser in the final moments to send the contest into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then stood as the hero, stopping decisive kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, the full-back, and Desire Doue all converted with composure for Paris Saint-Germain to seal a convincing penalty win.
The record winners PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a domestic double, have now won this competition for the twelfth time in the last 13 years.
