PSG has now won the prestigious cup on 14 different times.
The Parisian giants required a stoppage-time leveler followed by a perfect spot-kick decider to overcome Marseille in the Gulf and capture a record-extending fourth consecutive French Super Cup victory.
The Champions League holders appeared to be coasting towards a comfortable triumph in the showdown featuring the Ligue 1 winners and the French Cup holders after the French winger opened the net in the opening stages.
Yet, Marseille fired two times in the closing moments to seize a shock lead. First, Mason Greenwood scored from the penalty spot, before the defender unfortunately turned the ball into his own net for an own goal.
In a breathtaking twist of events, the Portuguese striker snatched a vital leveler in the final seconds to send the match into a deciding shootout. PSG goalkeeper Chevalier then emerged as the key figure, saving decisive attempts from Matt O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, the full-back, and Desire Doue all converted with composure for PSG to seal a convincing penalty victory.
The record champions Paris Saint-Germain, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a domestic double, have now won this trophy for the twelfth time in the last thirteen years.
