PSG has now claimed the prestigious cup on 14 separate times.
The Parisian giants required a dramatic equaliser followed by a successful penalty shootout to get past Marseille in Kuwait and capture a fourth straight Trophee des Champions title.
The European champions appeared to be coasting towards a straightforward triumph in the showdown between the Ligue 1 champions and the Coupe de France winners after Ousmane Dembele found the scoring early on.
However, the southern French side struck twice late to take a shock lead. Initially, Mason Greenwood converted from the spot-kick, before the defender unfortunately turned the ball into his own net for an own goal.
In a remarkable twist of fortune, Goncalo Ramos snatched a vital equaliser in the final moments to force the match into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the hero, stopping decisive kicks from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, the full-back, and Desire Doue all scored successfully for Paris Saint-Germain to seal a convincing penalty victory.
The record champions PSG, who met last season's Ligue 1 runners-up Marseille after completing a domestic double, have now lifted this competition for the twelfth time in the last 13 years.
