PSG has now won the prestigious cup on 14 separate occasions.
The Parisian giants required a stoppage-time leveler followed by a successful spot-kick decider to get past their arch-rivals in the Gulf and capture a fourth straight Trophee des Champions title.
The European champions seemed to be sailing towards a straightforward win in the match featuring the Ligue 1 winners and the French Cup holders after Ousmane Dembele found the net early on.
Yet, the southern French side fired two times in the closing moments to take a surprise advantage. Initially, Mason Greenwood scored from the penalty spot, before Willian Pacho inadvertently turned the ball into his own net for an own goal.
In a remarkable twist of fortune, Goncalo Ramos grabbed a crucial equaliser in the dying moments to send the match into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the hero, saving decisive kicks from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, the full-back, and Desire Doue all scored with composure for PSG to seal a 4-1 penalty win.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Olympique de Marseille after completing a domestic double, have now won this competition for the twelfth time in the past thirteen seasons.
