The Parisian club has now claimed the season-opening cup on fourteen separate occasions.
The Parisian giants required a stoppage-time leveler followed by a successful spot-kick decider to overcome Marseille in the Gulf and capture a fourth straight Trophee des Champions title.
The European champions appeared to be coasting towards a comfortable triumph in the match between the French league champions and the Coupe de France holders after the French winger found the net early on.
However, the southern French side fired twice late to seize a shock lead. 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 breathtaking turn of events, the Portuguese striker grabbed a vital leveler in the final moments to send the match into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then stood as the hero, saving crucial attempts from O'Riley and Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all converted with composure for PSG to complete a convincing penalty victory.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now won this competition for the 12th time in the last 13 seasons.
