The Parisian club has now secured the prestigious trophy on 14 separate occasions.
Paris Saint-Germain needed a dramatic leveler followed by a perfect penalty shootout to get past their arch-rivals in the Gulf and capture a record-extending fourth consecutive Trophee des Champions victory.
The Champions League holders appeared to be coasting towards a comfortable triumph in the showdown featuring the French league champions and the Coupe de France winners after Ousmane Dembele found the scoring in the opening stages.
However, the southern French side struck two times late to take a surprise lead. First, the English forward scored from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own-goal.
In a breathtaking turn of fortune, Goncalo Ramos snatched a crucial equaliser in the dying seconds to force the contest into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, saving crucial kicks from Matt O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and Desire Doue all converted successfully for Paris Saint-Germain to seal a 4-1 penalty win.
Now 14-time champions PSG, who met last season's Ligue 1 runners-up Marseille after completing a domestic double, have now won this trophy for the twelfth time in the past 13 years.
