PSG has now won the prestigious cup on fourteen separate times.
The Parisian giants required a stoppage-time equaliser followed by a perfect penalty shootout to get past Marseille in Kuwait and capture a fourth straight Trophee des Champions victory.
The Champions League holders seemed to be coasting towards a straightforward triumph in the showdown between the French league winners and the Coupe de France holders after Ousmane Dembele found the scoring early on.
However, the southern French side struck twice late to seize a shock advantage. First, Mason Greenwood scored from the penalty spot, before Willian Pacho inadvertently directed the ball into his own net for an own goal.
In a remarkable twist of events, Goncalo Ramos snatched a vital leveler in the final seconds to send the contest into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then stood as the key figure, saving decisive attempts from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all scored successfully for Paris Saint-Germain to seal a convincing penalty victory.
Now 14-time winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now won this trophy for the twelfth time in the last thirteen seasons.
