PSG has now secured the season-opening cup on 14 different times.
Paris Saint-Germain needed a stoppage-time equaliser followed by a successful penalty shootout to overcome their arch-rivals in the Gulf and capture a record-extending fourth consecutive French Super Cup title.
The European champions seemed to be sailing towards a straightforward win in the match featuring the French league winners and the French Cup holders after Ousmane Dembele found the net in the opening stages.
Yet, Marseille struck two times in the closing moments to take a shock advantage. First, Mason Greenwood converted from the spot-kick, before the defender unfortunately turned the ball into his own net for an own goal.
In a remarkable twist of events, Goncalo Ramos grabbed a vital leveler in the final seconds to force the match into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the hero, stopping crucial attempts from Matt O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted with composure for Paris Saint-Germain to complete a 4-1 shootout victory.
The record winners PSG, who met last season's Ligue 1 runners-up Marseille after completing a league and cup double, have now lifted this competition for the twelfth time in the past 13 seasons.
