PSG has now secured the prestigious cup on 14 different occasions.
The Parisian giants needed a dramatic leveler followed by a successful spot-kick decider to get past their arch-rivals in Kuwait and secure a record-extending fourth consecutive Trophee des Champions title.
The European champions appeared to be sailing towards a straightforward triumph in the match between the French league winners and the French Cup winners after Ousmane Dembele opened the net in the opening stages.
Yet, the southern French side fired two times late to seize a shock lead. Initially, the English forward scored from the spot-kick, before the defender inadvertently directed the ball into his own net for an own goal.
In a remarkable twist of events, the Portuguese striker grabbed a crucial leveler in the dying moments to force the contest into a deciding shootout. PSG goalkeeper Chevalier then emerged as the key figure, stopping decisive attempts from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all scored successfully for Paris Saint-Germain to complete a 4-1 shootout win.
Now 14-time champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after achieving a domestic double, have now lifted this trophy for the twelfth time in the last 13 seasons.