The Parisian club has now claimed the prestigious cup on fourteen separate occasions.
The Parisian giants needed a dramatic leveler followed by a successful penalty shootout to get past Marseille in the Gulf and capture a fourth straight French Super Cup victory.
The European champions seemed to be sailing towards a straightforward win in the match featuring the French league winners and the Coupe de France winners after the French winger opened the scoring early on.
However, Marseille struck twice late to take a shock lead. First, the English forward scored from the penalty spot, before the defender inadvertently turned the ball into his own net for an own goal.
In a remarkable twist of fortune, Goncalo Ramos snatched a crucial leveler in the final moments to send the match into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the key figure, stopping crucial attempts from O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, Nuno Mendes, and the young talent all scored successfully for PSG to complete a 4-1 penalty victory.
Now 14-time winners Paris Saint-Germain, who faced last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now won this competition for the twelfth time in the past thirteen years.
