PSG has now won the prestigious cup on 14 different times.
The Parisian giants needed a stoppage-time equaliser followed by a perfect spot-kick decider to overcome their arch-rivals in the Gulf and capture a fourth straight French Super Cup title.
The Champions League holders appeared to be coasting towards a comfortable triumph in the showdown featuring the Ligue 1 champions and the Coupe de France winners after the French winger opened the net in the opening stages.
Yet, the southern French side struck two times late to take a surprise lead. Initially, the English forward converted from the penalty spot, before the defender inadvertently turned the ball into his own net for an own-goal.
In a remarkable turn of fortune, the Portuguese striker grabbed a vital equaliser in the final moments to force the contest into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then stood as the hero, stopping decisive attempts from O'Riley and Traore.
In the shootout, Goncalo Ramos, the midfielder, Nuno Mendes, and the young talent all converted successfully for Paris Saint-Germain to complete a 4-1 penalty win.
The record champions PSG, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now won this competition for the 12th time in the last thirteen seasons.
