The Parisian club has now won the prestigious trophy on fourteen different occasions.
The Parisian giants needed a stoppage-time equaliser followed by a successful spot-kick decider to overcome Marseille in Kuwait and secure a fourth straight Trophee des Champions victory.
The European champions appeared to be sailing towards a comfortable win in the showdown between the Ligue 1 winners and the French Cup winners after Ousmane Dembele opened the scoring early on.
Yet, the southern French side fired twice late to take a surprise lead. Initially, the English forward scored from the spot-kick, before the defender unfortunately directed the ball into his own net for an own-goal.
In a remarkable twist of events, the Portuguese striker grabbed a crucial equaliser in the dying seconds to force the contest into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the hero, saving crucial kicks from O'Riley and Traore.
From the spot, Ramos, the midfielder, the full-back, and Desire Doue all converted with composure for Paris Saint-Germain to complete a convincing shootout win.
The record champions PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now won this trophy for the 12th time in the past thirteen years.