PSG has now claimed the prestigious cup on 14 separate times.
The Parisian giants required a dramatic equaliser followed by a perfect spot-kick decider to get past 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 showdown between the Ligue 1 winners and the Coupe de France winners after the French winger opened the scoring early on.
Yet, the southern French side fired twice late to take a shock lead. First, the English forward scored from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a breathtaking turn of fortune, the Portuguese striker grabbed a crucial equaliser in the final moments to send the contest into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the hero, saving decisive attempts from O'Riley and Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored successfully for Paris Saint-Germain to complete a convincing penalty victory.
Now 14-time winners Paris Saint-Germain, who faced last season's Ligue 1 runners-up Marseille after achieving a domestic double, have now won this competition for the twelfth time in the last thirteen seasons.
