PSG has now won the prestigious trophy on 14 separate times.
The Parisian giants required a stoppage-time equaliser 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 straightforward triumph in the match featuring the French league winners and the Coupe de France winners after the French winger found the scoring in the opening stages.
However, Marseille fired twice in the closing moments to take a shock advantage. First, Mason Greenwood scored from the penalty spot, before the defender unfortunately directed the ball into his own net for an own goal.
In a breathtaking twist of fortune, the Portuguese striker grabbed a vital equaliser in the final moments to force the contest into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, stopping crucial kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all scored with composure for Paris Saint-Germain to complete a 4-1 penalty win.
Now 14-time winners PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now lifted this trophy for the 12th time in the last 13 years.
