PSG has now claimed the prestigious trophy on fourteen different times.
Paris Saint-Germain needed a stoppage-time equaliser followed by a successful spot-kick decider to get past Marseille in Kuwait and secure a fourth straight Trophee des Champions title.
The Champions League holders appeared to be sailing towards a straightforward triumph in the showdown featuring the Ligue 1 champions and the Coupe de France holders after the French winger opened the net early on.
Yet, the southern French side fired twice in the closing moments to take a shock advantage. First, Mason Greenwood converted from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a remarkable twist of fortune, Goncalo Ramos snatched a vital equaliser in the dying seconds to send the contest into a deciding shootout. PSG goalkeeper Chevalier then stood as the key figure, saving crucial kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all converted with composure for PSG to seal a convincing shootout victory.
Now 14-time champions PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now lifted this trophy for the twelfth time in the last thirteen seasons.
