The Parisian club has now claimed the prestigious trophy on 14 different occasions.
Paris Saint-Germain needed a stoppage-time equaliser followed by a successful spot-kick decider to get past Marseille in the Gulf and capture a record-extending fourth consecutive French Super Cup title.
The European champions seemed to be coasting towards a straightforward triumph in the match between the Ligue 1 winners and the French Cup holders after Ousmane Dembele found the scoring early on.
Yet, the southern French side struck twice in the closing moments to take a shock advantage. First, Mason Greenwood scored from the spot-kick, before the defender inadvertently turned the ball into his own net for an own goal.
In a remarkable turn of fortune, the Portuguese striker snatched a crucial equaliser in the dying moments to force the match into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the key figure, stopping decisive attempts from Matt O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored with composure for PSG to complete a 4-1 shootout victory.
The record champions Paris Saint-Germain, who met last season's Ligue 1 runners-up Olympique de Marseille after completing a league and cup double, have now won this trophy for the 12th time in the past thirteen seasons.
