PSG has now claimed the prestigious trophy on fourteen separate times.
Paris Saint-Germain required a stoppage-time equaliser followed by a successful penalty shootout to overcome their arch-rivals in Kuwait and secure a fourth straight Trophee des Champions victory.
The European champions seemed to be coasting towards a straightforward triumph in the match between the Ligue 1 winners and the French Cup holders after the French winger found the net in the opening stages.
Yet, the southern French side struck twice late to seize a shock lead. Initially, Mason Greenwood converted from the penalty spot, before the defender inadvertently turned the ball into his own net for an own goal.
In a breathtaking turn of events, the Portuguese striker snatched a crucial equaliser in the dying moments to send the contest into a deciding shootout. PSG goalkeeper Lucas Chevalier then emerged as the hero, saving decisive kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all converted with composure for Paris Saint-Germain to seal a convincing shootout win.
Now 14-time winners PSG, who faced last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now lifted this trophy for the 12th time in the past 13 seasons.
