PSG has now claimed the season-opening trophy on fourteen separate times.
The Parisian giants required a stoppage-time leveler followed by a successful penalty shootout to get past their arch-rivals in the Gulf and secure a fourth straight Trophee des Champions victory.
The Champions League holders seemed to be coasting towards a comfortable triumph in the showdown between the French league winners and the Coupe de France holders after Ousmane Dembele found the net early on.
However, the southern French side fired two times in the closing moments to seize a shock advantage. Initially, Mason Greenwood scored from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a breathtaking twist of fortune, the Portuguese striker snatched a crucial equaliser in the dying seconds to force the match into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the hero, saving decisive kicks from O'Riley and Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all converted successfully for PSG to seal a convincing shootout victory.
Now 14-time winners Paris Saint-Germain, who met last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now lifted this competition for the 12th time in the past 13 years.
