The Parisian club has now secured the prestigious cup on fourteen different occasions.
Paris Saint-Germain needed a stoppage-time equaliser followed by a perfect spot-kick decider to overcome their arch-rivals in the Gulf and capture a fourth straight Trophee des Champions title.
The European champions appeared to be coasting towards a straightforward triumph in the showdown between the Ligue 1 winners and the Coupe de France winners after Ousmane Dembele opened the scoring in the opening stages.
However, the southern French side struck two times in the closing moments to seize a shock lead. First, the English forward converted from the spot-kick, before the defender inadvertently directed the ball into his own net for an own goal.
In a remarkable turn of fortune, Goncalo Ramos grabbed a vital equaliser in the dying seconds to send the match into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then stood as the key figure, saving decisive kicks from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and the young talent all converted with composure for Paris Saint-Germain to seal a 4-1 shootout victory.
Now 14-time champions PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now won this trophy for the 12th time in the last 13 seasons.
