PSG has now won the prestigious cup on 14 different times.
Paris Saint-Germain required a stoppage-time leveler followed by a perfect penalty shootout to get past Marseille in Kuwait and secure a fourth straight Trophee des Champions victory.
The Champions League holders appeared to be coasting towards a comfortable triumph in the match featuring the Ligue 1 winners and the Coupe de France winners after the French winger found the net in the opening stages.
However, the southern French side fired two times in the closing moments to take a shock lead. Initially, Mason Greenwood scored from the spot-kick, before Willian Pacho inadvertently directed the ball into his own net for an own goal.
In a breathtaking twist of fortune, Goncalo Ramos grabbed a crucial equaliser in the final seconds to force the match into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the key figure, saving decisive kicks from O'Riley and Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and the young talent all scored successfully for Paris Saint-Germain to complete a 4-1 penalty victory.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now lifted this competition for the 12th time in the past 13 seasons.
