The Parisian club has now won the season-opening trophy on 14 different times.
The Parisian giants needed a stoppage-time leveler followed by a successful spot-kick decider to get past Marseille in Kuwait and secure a record-extending fourth consecutive Trophee des Champions victory.
The Champions League holders appeared to be sailing towards a comfortable triumph in the showdown between the Ligue 1 champions and the Coupe de France winners after Ousmane Dembele opened the scoring early on.
Yet, Marseille fired two times late to take a shock lead. Initially, the English forward scored from the spot-kick, before Willian Pacho inadvertently directed the ball into his own net for an own-goal.
In a remarkable turn of events, Goncalo Ramos grabbed a vital leveler in the final seconds to send the contest into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then stood as the key figure, stopping crucial attempts from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all scored successfully for Paris Saint-Germain to seal a convincing penalty win.
The record champions PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a league and cup double, have now lifted this competition for the twelfth time in the past thirteen seasons.
