The Parisian club has now won the prestigious cup on 14 separate times.
The Parisian giants needed a dramatic equaliser followed by a perfect spot-kick decider to get past their arch-rivals in Kuwait and capture a record-extending fourth consecutive French Super Cup victory.
The Champions League holders seemed to be coasting towards a straightforward triumph in the match featuring the French league champions and the Coupe de France winners after the French winger opened the scoring in the opening stages.
However, Marseille fired two times late to take a surprise advantage. Initially, the English forward converted from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own-goal.
In a breathtaking turn of events, Goncalo Ramos grabbed a vital leveler in the final moments to send the match into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the hero, stopping crucial kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, Nuno Mendes, and the young talent all scored successfully for Paris Saint-Germain to complete a 4-1 shootout win.
The record winners PSG, 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 twelfth time in the last 13 seasons.
