The Parisian club has now claimed the season-opening cup on fourteen different times.
The Parisian giants required a stoppage-time leveler followed by a perfect penalty shootout to get past their arch-rivals in the Gulf and capture a fourth straight Trophee des Champions title.
The Champions League holders appeared to be sailing towards a straightforward win in the showdown featuring the French league champions and the French Cup winners after Ousmane Dembele found the scoring early on.
However, Marseille struck two times late to seize a shock advantage. First, the English forward converted from the spot-kick, before the defender unfortunately directed the ball into his own net for an own goal.
In a breathtaking twist of events, Goncalo Ramos snatched a crucial equaliser in the dying seconds to send the contest into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the hero, saving decisive attempts from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored with composure for PSG to seal a 4-1 shootout victory.
The record champions PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a domestic double, have now won this trophy for the 12th time in the past thirteen seasons.
