PSG has now secured the season-opening trophy on 14 different times.
The Parisian giants required a dramatic leveler followed by a perfect penalty shootout to overcome their arch-rivals in Kuwait and capture a fourth straight Trophee des Champions title.
The Champions League holders seemed to be sailing towards a comfortable win in the showdown featuring the French league champions and the Coupe de France holders after Ousmane Dembele found the net in the opening stages.
However, the southern French side fired twice in the closing moments to seize a shock lead. First, the English forward converted from the penalty spot, before the defender inadvertently turned the ball into his own net for an own-goal.
In a remarkable twist of events, Goncalo Ramos snatched a crucial leveler in the dying seconds to send the contest into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the hero, stopping crucial attempts from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, the full-back, and Desire Doue all scored with composure for Paris Saint-Germain to seal a convincing shootout win.
Now 14-time winners PSG, who faced last season's Ligue 1 runners-up Marseille after completing a domestic double, have now won this trophy for the 12th time in the past 13 years.
