The Parisian club has now won the season-opening trophy on 14 separate times.
The Parisian giants needed a stoppage-time leveler followed by a successful spot-kick decider to get past Marseille in Kuwait and secure a fourth straight Trophee des Champions title.
The European champions seemed to be coasting towards a straightforward win in the match featuring the French league winners and the Coupe de France holders after the French winger opened the net early on.
However, the southern French side struck two times late to take a surprise advantage. First, the English forward scored from the penalty spot, before the defender inadvertently directed the ball into his own net for an own-goal.
In a breathtaking twist of events, the Portuguese striker grabbed a vital leveler in the final moments to send the contest into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the key figure, stopping crucial kicks from O'Riley and Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored with composure for Paris Saint-Germain to complete a convincing penalty win.
Now 14-time champions PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a domestic double, have now lifted this trophy for the twelfth time in the past thirteen seasons.