PSG has now won the season-opening cup on 14 different times.
Paris Saint-Germain needed a stoppage-time leveler followed by a successful penalty shootout to overcome their arch-rivals in the Gulf and secure a fourth straight Trophee des Champions title.
The European champions appeared to be sailing towards a straightforward win in the showdown between the French league champions and the Coupe de France holders after the French winger found the net in the opening stages.
However, the southern French side struck twice late to take a shock lead. First, the English forward scored from the penalty spot, before the defender inadvertently directed the ball into his own net for an own goal.
In a remarkable turn of events, Goncalo Ramos grabbed a vital equaliser in the final moments to send the contest into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then stood as the key figure, stopping crucial attempts from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, the full-back, and the young talent all scored successfully for PSG to seal a convincing penalty victory.
The record champions PSG, who faced last season's Ligue 1 runners-up Olympique de Marseille after achieving a league and cup double, have now lifted this trophy for the twelfth time in the past thirteen seasons.