PSG has now secured the season-opening trophy on fourteen different times.
The Parisian giants needed a dramatic leveler followed by a perfect penalty shootout to overcome Marseille in the Gulf and capture a record-extending fourth consecutive Trophee des Champions title.
The European champions appeared to be sailing towards a straightforward win in the showdown between the Ligue 1 champions and the Coupe de France winners after the French winger opened the scoring early on.
Yet, the southern French side fired two times in the closing moments to seize a surprise lead. Initially, the English forward scored from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own goal.
In a remarkable twist of fortune, Goncalo Ramos grabbed a crucial equaliser in the dying moments to force the match into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, saving decisive attempts from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all scored successfully for Paris Saint-Germain to seal a convincing penalty victory.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Olympique de Marseille after completing a domestic double, have now won this competition for the 12th time in the last thirteen seasons.