The Parisian club has now claimed the prestigious trophy on 14 different times.
The Parisian giants needed a stoppage-time leveler followed by a perfect spot-kick decider to overcome their arch-rivals in the Gulf and secure a fourth straight Trophee des Champions victory.
The European champions seemed to be coasting towards a straightforward triumph in the showdown featuring the Ligue 1 champions 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 take a surprise advantage. Initially, the English forward scored from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own-goal.
In a remarkable turn of fortune, the Portuguese striker grabbed a crucial equaliser in the dying moments to force the match into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then stood as the hero, stopping crucial attempts from O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, the full-back, and Desire Doue all converted with composure for Paris Saint-Germain to complete a 4-1 penalty win.
Now 14-time champions 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 13 years.
