The Parisian club has now won the prestigious 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 capture a fourth straight Trophee des Champions victory.
The Champions League holders seemed to be coasting towards a comfortable triumph in the showdown featuring the Ligue 1 champions and the Coupe de France holders after the French winger opened the net in the opening stages.
However, the southern French side fired two times late to seize a shock advantage. Initially, the English forward converted from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a remarkable twist of fortune, the Portuguese striker grabbed a vital equaliser in the dying seconds to force the match into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the hero, stopping crucial attempts from O'Riley and Traore.
In the shootout, Goncalo Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted with composure for Paris Saint-Germain to complete a convincing penalty win.
The record winners Paris Saint-Germain, who met last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now won this trophy for the twelfth time in the past thirteen seasons.
