The Parisian club has now won the prestigious trophy on fourteen separate occasions.
Paris Saint-Germain required a dramatic equaliser followed by a perfect spot-kick decider to get past Marseille in the Gulf and secure a fourth straight French Super Cup title.
The Champions League holders appeared to be coasting towards a comfortable win in the match between the Ligue 1 winners and the French Cup holders after Ousmane Dembele found the scoring early on.
However, Marseille fired two times in the closing moments to seize a shock lead. First, Mason Greenwood scored from the penalty spot, before the defender inadvertently turned the ball into his own net for an own goal.
In a remarkable turn of events, Goncalo Ramos snatched a crucial equaliser in the final moments to send the match into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, stopping decisive attempts from O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, Nuno Mendes, and Desire Doue all scored with composure for Paris Saint-Germain to seal a convincing penalty victory.
The record winners PSG, who faced last season's Ligue 1 runners-up Olympique de Marseille after achieving a league and cup double, have now won this trophy for the twelfth time in the past 13 seasons.
