PSG has now secured the prestigious trophy on 14 different times.
The Parisian giants required a stoppage-time equaliser followed by a perfect spot-kick decider to overcome Marseille in the Gulf and capture a fourth straight Trophee des Champions victory.
The European champions seemed to be sailing towards a comfortable triumph in the showdown between the Ligue 1 champions and the Coupe de France winners after the French winger opened the net early on.
Yet, the southern French side struck two times late to take a surprise advantage. Initially, the English forward converted from the spot-kick, before Willian Pacho unfortunately directed the ball into his own net for an own goal.
In a remarkable turn of fortune, Goncalo Ramos grabbed a vital leveler in the final seconds to send the contest into a deciding shootout. PSG goalkeeper Chevalier then emerged as the key figure, stopping crucial kicks from O'Riley and Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted successfully for Paris Saint-Germain to complete a 4-1 penalty win.
The record champions PSG, who faced last season's Ligue 1 runners-up Olympique de Marseille after completing a league and cup double, have now won this trophy for the twelfth time in the past thirteen seasons.
