PSG has now claimed the season-opening trophy on fourteen separate occasions.
Paris Saint-Germain required a stoppage-time leveler followed by a successful spot-kick decider to overcome Marseille in the Gulf and capture a fourth straight Trophee des Champions title.
The Champions League holders seemed to be coasting towards a straightforward triumph in the match featuring the Ligue 1 winners and the Coupe de France holders after Ousmane Dembele opened the scoring early on.
Yet, Marseille fired twice in the closing moments to take a shock advantage. First, the English forward scored from the spot-kick, before Willian Pacho inadvertently directed the ball into his own net for an own-goal.
In a remarkable twist of events, the Portuguese striker snatched a crucial equaliser in the dying seconds to send the match into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the hero, saving crucial attempts from O'Riley and Traore.
In the shootout, Ramos, Vitinha, the full-back, and Desire Doue all scored with composure for PSG to complete a convincing shootout victory.
The record winners PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now won this trophy for the 12th time in the last 13 seasons.