The Parisian club has now won the prestigious trophy on fourteen different occasions.
Paris Saint-Germain needed a stoppage-time leveler followed by a successful penalty shootout to overcome Marseille in Kuwait and secure a record-extending fourth consecutive French Super Cup victory.
The Champions League holders seemed to be sailing towards a comfortable triumph in the showdown featuring the Ligue 1 champions and the French Cup holders after the French winger opened the net in the opening stages.
However, Marseille fired two times late to take a shock advantage. Initially, Mason Greenwood converted from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a breathtaking twist of events, the Portuguese striker grabbed a crucial equaliser in the dying seconds to send the match into a penalty shootout. PSG goalkeeper Chevalier then emerged as the hero, saving crucial attempts from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, Nuno Mendes, and the young talent all scored successfully for PSG to seal a 4-1 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 won this competition for the 12th time in the past thirteen years.