PSG has now won the season-opening trophy on 14 separate occasions.
The Parisian giants needed a stoppage-time leveler followed by a perfect penalty shootout to get past their arch-rivals in the Gulf and capture a fourth straight Trophee des Champions victory.
The European champions appeared to be coasting towards a comfortable win in the showdown between the French league winners and the Coupe de France holders after Ousmane Dembele opened the scoring early on.
Yet, the southern French side struck twice late to take a shock lead. First, Mason Greenwood scored from the penalty spot, before Willian Pacho unfortunately turned the ball into his own net for an own-goal.
In a breathtaking turn of events, the Portuguese striker grabbed a crucial leveler in the dying moments to send the contest into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the key figure, saving decisive kicks from O'Riley and Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and the young talent all converted successfully for PSG to complete a 4-1 penalty victory.
Now 14-time winners Paris Saint-Germain, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now lifted this competition for the twelfth time in the last thirteen years.
