PSG has now claimed the season-opening cup on 14 separate times.
Paris Saint-Germain needed a stoppage-time leveler followed by a successful spot-kick decider to overcome their arch-rivals in the Gulf and capture a fourth straight Trophee des Champions victory.
The European champions appeared to be coasting towards a straightforward win in the showdown between the French league champions and the Coupe de France winners after Ousmane Dembele opened the scoring in the opening stages.
Yet, the southern French side fired two times in the closing moments to seize a shock advantage. Initially, the English forward converted from the penalty spot, before the defender inadvertently turned the ball into his own net for an own-goal.
In a breathtaking twist of fortune, the Portuguese striker snatched a vital equaliser in the dying seconds to send the match into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, saving crucial kicks from Matt O'Riley and Traore.
From the spot, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all converted successfully for PSG to complete a 4-1 penalty victory.
The record champions PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now lifted this trophy for the 12th time in the past thirteen seasons.
