The Parisian club has now secured the prestigious trophy on 14 separate times.
Paris Saint-Germain required a stoppage-time leveler followed by a perfect penalty shootout to overcome Marseille in Kuwait and capture a fourth straight Trophee des Champions title.
The European champions seemed to be coasting towards a comfortable win in the showdown between the French league winners and the French Cup winners after the French winger opened the net in the opening stages.
Yet, the southern French side struck twice in the closing moments to take a shock advantage. Initially, Mason Greenwood scored from the spot-kick, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a remarkable twist of fortune, the Portuguese striker snatched a vital equaliser in the final moments to force the match into a deciding shootout. PSG goalkeeper Chevalier then stood as the hero, stopping crucial kicks from O'Riley and Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and the young talent all converted successfully for Paris Saint-Germain to seal a convincing penalty victory.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 runners-up Marseille after completing a domestic double, have now won this trophy for the twelfth time in the past thirteen seasons.
