The Parisian club has now claimed the prestigious trophy on fourteen different occasions.
Paris Saint-Germain required a stoppage-time leveler followed by a perfect penalty shootout to get past their arch-rivals in Kuwait and capture a fourth straight Trophee des Champions title.
The Champions League holders seemed to be sailing towards a straightforward triumph in the showdown between the Ligue 1 winners and the Coupe de France holders after the French winger opened the scoring in the opening stages.
However, the southern French side struck twice in the closing moments to seize a surprise lead. Initially, the English forward converted from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own goal.
In a breathtaking turn of events, Goncalo Ramos grabbed a crucial leveler in the dying moments to force the contest into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the key figure, saving decisive kicks from O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, the full-back, and Desire Doue all converted successfully for Paris Saint-Germain to complete a convincing shootout victory.
Now 14-time winners PSG, who faced last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now lifted this trophy for the 12th time in the past 13 seasons.
