The Parisian club has now claimed the prestigious cup on 14 different times.
Paris Saint-Germain needed a dramatic equaliser followed by a perfect penalty shootout to overcome their arch-rivals in the Gulf and secure a fourth straight French Super Cup title.
The Champions League holders seemed to be sailing towards a comfortable triumph in the match featuring the French league champions and the Coupe de France winners after the French winger found the scoring in the opening stages.
Yet, the southern French side fired twice late to take a shock lead. First, the English forward scored 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, the Portuguese striker grabbed a crucial equaliser in the dying seconds to send the contest into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the key figure, stopping decisive attempts from O'Riley and Traore.
From the spot, Ramos, the midfielder, Nuno Mendes, and Desire Doue all scored successfully for PSG to seal a 4-1 penalty win.
Now 14-time winners Paris Saint-Germain, who met last season's Ligue 1 runners-up Marseille after achieving a league and cup double, have now won this competition for the 12th time in the last 13 seasons.
