PSG has now claimed the prestigious cup on 14 different times.
The Parisian giants required a dramatic leveler followed by a successful penalty shootout to overcome their arch-rivals in Kuwait and capture a fourth straight Trophee des Champions title.
The European champions appeared to be coasting towards a comfortable triumph in the match between the French league winners and the French Cup holders after Ousmane Dembele found the scoring early on.
Yet, the southern French side struck twice in the closing moments to take a shock lead. First, the English forward scored from the penalty spot, before the defender unfortunately turned the ball into his own net for an own goal.
In a breathtaking twist of fortune, the Portuguese striker snatched a crucial equaliser in the dying moments to force the match into a deciding shootout. PSG goalkeeper Chevalier then stood as the hero, stopping crucial kicks from Matt O'Riley and Traore.
From the spot, Ramos, the midfielder, the full-back, and Desire Doue all scored with composure for Paris Saint-Germain to seal a 4-1 shootout victory.
The record winners 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 last 13 years.
