PSG has now won the season-opening trophy on 14 different occasions.
Paris Saint-Germain needed a dramatic leveler followed by a successful spot-kick decider to overcome Marseille in the Gulf and secure a record-extending fourth consecutive French Super Cup victory.
The Champions League holders seemed to be coasting towards a comfortable win in the match featuring the Ligue 1 champions and the French Cup holders after Ousmane Dembele opened the scoring early on.
However, the southern French side struck twice late to seize a shock lead. First, Mason Greenwood scored from the penalty spot, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a breathtaking turn of fortune, Goncalo Ramos 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 decisive attempts from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted with composure for PSG to complete a convincing shootout victory.
The record winners Paris Saint-Germain, who met last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now lifted this trophy for the twelfth time in the last 13 years.
