PSG has now secured the season-opening cup on 14 different times.
The Parisian giants required a dramatic leveler followed by a successful spot-kick decider to overcome Marseille in the Gulf and secure a fourth straight French Super Cup title.
The European champions seemed to be coasting towards a straightforward win in the showdown featuring the Ligue 1 winners and the Coupe de France holders after the French winger opened the net in the opening stages.
However, the southern French side fired twice in the closing moments to take a shock lead. 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 remarkable twist of events, the Portuguese striker grabbed a crucial leveler in the dying moments to send the match into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then stood as the key figure, saving crucial kicks from Matt O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted successfully for PSG to seal a 4-1 shootout win.
The record champions PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now won this trophy for the 12th time in the last 13 seasons.
