The Parisian club has now claimed the season-opening trophy on 14 different times.
Paris Saint-Germain required a stoppage-time leveler followed by a successful spot-kick decider to overcome their arch-rivals in the Gulf and capture a fourth straight French Super Cup victory.
The European champions seemed to be coasting towards a straightforward win in the match between the Ligue 1 winners and the French Cup holders after Ousmane Dembele opened the scoring in the opening stages.
However, Marseille struck twice late to seize a shock advantage. Initially, Mason Greenwood converted from the penalty spot, before Willian Pacho inadvertently turned the ball into his own net for an own-goal.
In a breathtaking twist of fortune, the Portuguese striker grabbed a vital leveler in the dying seconds to send the match into a deciding shootout. PSG goalkeeper Chevalier then emerged as the key figure, stopping decisive attempts from O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, the full-back, and the young talent all scored with composure for Paris Saint-Germain to seal a convincing penalty win.
The record winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now lifted this trophy for the 12th time in the last thirteen seasons.
