PSG has now secured the season-opening cup on 14 separate occasions.
The Parisian giants needed a stoppage-time leveler followed by a perfect penalty shootout to overcome Marseille in Kuwait and capture a fourth straight Trophee des Champions victory.
The Champions League holders seemed to be coasting towards a straightforward win in the showdown between the Ligue 1 winners and the French Cup holders after Ousmane Dembele found the net in the opening stages.
However, the southern French side fired twice late to take a shock advantage. 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 breathtaking twist of fortune, the Portuguese striker grabbed a vital leveler in the dying moments to send the contest into a deciding shootout. PSG goalkeeper Chevalier then stood as the key figure, stopping decisive kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and Desire Doue all scored with composure for Paris Saint-Germain to seal a convincing penalty victory.
The record winners PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after completing a league and cup double, have now won this trophy for the twelfth time in the past thirteen seasons.
