The Parisian club has now claimed the prestigious cup on 14 different occasions.
The Parisian giants needed a dramatic equaliser followed by a successful spot-kick decider to overcome their arch-rivals in the Gulf and secure a fourth straight Trophee des Champions victory.
The European champions appeared to be coasting towards a comfortable triumph in the showdown featuring the French league winners and the Coupe de France holders after Ousmane Dembele opened the net in the opening stages.
Yet, the southern French side fired twice in the closing moments to seize a shock lead. First, Mason Greenwood scored from the penalty spot, before the defender inadvertently directed the ball into his own net for an own-goal.
In a breathtaking turn of events, the Portuguese striker grabbed a crucial equaliser in the dying moments to send the match into a penalty shootout. PSG goalkeeper Chevalier then emerged as the hero, stopping crucial attempts from Matt O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, Nuno Mendes, and the young talent all scored with composure for Paris Saint-Germain to complete a 4-1 shootout victory.
The record 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 twelfth time in the past 13 seasons.
