PSG has now secured the prestigious cup 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 title.
The Champions League holders seemed to be sailing towards a straightforward win in the showdown featuring the French league winners and the French Cup holders after Ousmane Dembele opened the net early on.
Yet, the southern French side struck twice in the closing moments to seize a surprise lead. First, the English forward converted from the penalty spot, before the defender inadvertently turned the ball into his own net for an own goal.
In a breathtaking twist of events, the Portuguese striker snatched a vital leveler in the final moments to force the contest into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the key figure, stopping crucial kicks from O'Riley and Traore.
In the shootout, Ramos, Vitinha, the full-back, and Desire Doue all scored with composure for Paris Saint-Germain to complete a convincing shootout victory.
The record winners Paris Saint-Germain, who faced 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 past 13 years.
