PSG has now claimed the prestigious cup on 14 separate occasions.
Paris Saint-Germain required a stoppage-time equaliser followed by a successful penalty shootout to get past their arch-rivals in the Gulf and secure a fourth straight Trophee des Champions title.
The Champions League holders seemed to be coasting towards a straightforward win in the showdown between 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 struck two times in the closing moments to seize a surprise lead. Initially, Mason Greenwood scored from the penalty spot, before the defender unfortunately directed the ball into his own net for an own-goal.
In a breathtaking turn of events, the Portuguese striker grabbed a vital equaliser in the final moments to send the contest into a deciding shootout. PSG goalkeeper Chevalier then stood as the key figure, saving decisive kicks from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, Nuno Mendes, and Desire Doue all converted with composure for PSG to seal a convincing penalty win.
The record winners PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a league and cup double, have now won this competition for the 12th time in the past 13 seasons.
