PSG has now won the season-opening trophy on 14 separate times.
The Parisian giants required a dramatic leveler followed by a perfect spot-kick decider to get past their arch-rivals in Kuwait and capture a fourth straight Trophee des Champions title.
The Champions League holders seemed to be coasting towards a straightforward triumph in the match between the French league champions and the Coupe de France winners after the French winger found the scoring early on.
However, the southern French side fired two times late to take a shock advantage. Initially, Mason Greenwood converted from the spot-kick, before the defender inadvertently directed the ball into his own net for an own-goal.
In a remarkable turn of fortune, Goncalo Ramos snatched a vital equaliser in the dying seconds to force the contest into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the key figure, stopping decisive kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all converted successfully for Paris Saint-Germain to complete a convincing penalty victory.
Now 14-time champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Marseille after completing a league and cup double, have now won this trophy for the 12th time in the last 13 seasons.
