The Parisian club has now secured the season-opening trophy on 14 separate times.
The Parisian giants needed a dramatic leveler followed by a successful penalty shootout to get past their arch-rivals in the Gulf and secure a fourth straight Trophee des Champions victory.
The Champions League holders appeared to be coasting towards a comfortable triumph in the showdown between the French league champions and the Coupe de France winners after Ousmane Dembele opened the scoring early on.
Yet, Marseille struck two times in the closing moments to take a surprise advantage. First, the English forward scored from the penalty spot, before Willian Pacho inadvertently 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 seconds to send the match into a penalty shootout. PSG goalkeeper Chevalier then emerged as the hero, saving 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 convincing shootout victory.
The record winners PSG, who met last season's Ligue 1 runners-up Marseille after achieving a league and cup double, have now lifted this competition for the 12th time in the last thirteen seasons.
