The Parisian club has now won the season-opening trophy on 14 separate times.
Paris Saint-Germain needed a dramatic leveler followed by a perfect penalty shootout to get past Marseille in the Gulf and secure a record-extending fourth consecutive French Super Cup victory.
The Champions League holders seemed to be sailing towards a straightforward win in the match between the Ligue 1 champions and the Coupe de France winners after Ousmane Dembele opened the scoring in the opening stages.
However, the southern French side fired twice in the closing moments to take a surprise lead. Initially, Mason Greenwood converted from the spot-kick, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a breathtaking turn of events, the Portuguese striker snatched a vital equaliser in the dying moments to force the match into a penalty shootout. PSG goalkeeper Chevalier then stood as the hero, stopping crucial kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, the full-back, and the young talent all converted successfully for Paris Saint-Germain to complete a 4-1 penalty win.
The record winners PSG, who faced last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now won this competition for the twelfth time in the past 13 years.
