The Parisian club has now won the season-opening cup on 14 different occasions.
The Parisian giants needed a dramatic leveler followed by a perfect spot-kick decider to overcome Marseille in Kuwait and secure a fourth straight Trophee des Champions victory.
The European champions appeared to be sailing towards a comfortable triumph in the showdown featuring the Ligue 1 champions and the French Cup winners after the French winger opened the scoring in the opening stages.
Yet, Marseille fired twice in the closing moments to take a surprise advantage. First, 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 twist of events, Goncalo Ramos snatched a crucial equaliser in the dying seconds to send the contest into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the hero, saving crucial kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and Desire Doue all converted with composure for PSG to seal a convincing shootout victory.
Now 14-time winners Paris Saint-Germain, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now lifted this competition for the 12th time in the past thirteen seasons.
