PSG has now won the prestigious cup on fourteen different occasions.
Paris Saint-Germain required a stoppage-time leveler followed by a perfect penalty shootout to get past Marseille in Kuwait and secure a record-extending fourth consecutive French Super Cup title.
The Champions League holders seemed to be coasting towards a straightforward win in the match between the Ligue 1 winners and the French Cup winners after Ousmane Dembele found the scoring early on.
Yet, Marseille fired twice in the closing moments to take a shock lead. Initially, Mason Greenwood 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 snatched a crucial equaliser in the dying seconds to send the contest into a deciding shootout. PSG goalkeeper Chevalier then emerged as the hero, saving decisive attempts from Matt O'Riley and Traore.
From the spot, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all scored with composure for PSG to complete a convincing shootout victory.
Now 14-time winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now lifted this trophy for the twelfth time in the last thirteen seasons.