PSG has now secured the prestigious trophy on fourteen different times.
Paris Saint-Germain required a stoppage-time equaliser followed by a successful spot-kick decider to get past their arch-rivals in the Gulf and secure a fourth straight Trophee des Champions title.
The Champions League holders appeared to be coasting towards a comfortable win in the showdown featuring the French league champions and the Coupe de France winners after the French winger found the scoring early on.
However, the southern French side fired two times late to take a surprise advantage. Initially, the English forward converted from the penalty spot, before the defender inadvertently directed the ball into his own net for an own goal.
In a remarkable twist of fortune, Goncalo Ramos snatched a vital equaliser in the dying moments to force the contest into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the hero, saving decisive attempts from Matt O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all scored successfully for PSG to complete a convincing shootout victory.
Now 14-time champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Marseille after achieving a domestic double, have now won this trophy for the twelfth time in the past 13 seasons.
