The Parisian club has now claimed the prestigious cup on 14 different times.
The Parisian giants required a stoppage-time leveler followed by a successful spot-kick decider to get past Marseille in the Gulf and secure a fourth straight Trophee des Champions victory.
The European champions seemed to be coasting towards a comfortable win in the showdown between the French league winners and the Coupe de France winners after the French winger opened the net in the opening stages.
However, Marseille fired twice in the closing moments to seize a shock lead. First, Mason Greenwood scored from the spot-kick, before the defender 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 match into a penalty shootout. PSG goalkeeper Lucas Chevalier then stood as the key figure, saving crucial kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, Nuno Mendes, and the young talent all converted with composure for Paris Saint-Germain to complete a convincing shootout victory.
Now 14-time champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now won this trophy for the twelfth time in the last 13 seasons.
