PSG has now secured the prestigious trophy on 14 separate occasions.
Paris Saint-Germain required a stoppage-time equaliser followed by a perfect spot-kick decider to get past their arch-rivals in Kuwait and capture a fourth straight Trophee des Champions victory.
The European champions appeared to be sailing towards a straightforward win in the showdown featuring the French league champions and the French Cup holders after Ousmane Dembele found the net early on.
Yet, the southern French side fired two times in the closing moments to seize a surprise lead. First, the English forward converted from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a remarkable turn of fortune, Goncalo Ramos grabbed a vital equaliser in the dying moments to send the match into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then stood as the hero, stopping decisive attempts from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored with composure for Paris Saint-Germain to complete a convincing shootout win.
Now 14-time champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Marseille after completing a domestic double, have now won this trophy for the twelfth time in the last 13 seasons.
