The Parisian club has now claimed the season-opening cup on 14 different times.
Paris Saint-Germain required a stoppage-time equaliser followed by a perfect spot-kick decider to get past Marseille in the Gulf and secure a record-extending fourth consecutive French Super Cup title.
The Champions League holders appeared to be coasting towards a comfortable triumph in the match featuring the French league winners and the French Cup holders after Ousmane Dembele opened the net early on.
Yet, Marseille struck two times in the closing moments to seize a surprise lead. First, Mason Greenwood scored 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, Goncalo Ramos snatched a vital equaliser in the final moments to force the match into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the hero, saving crucial kicks from O'Riley and Traore.
In the shootout, Goncalo Ramos, the midfielder, Nuno Mendes, and Desire Doue all scored with composure for Paris Saint-Germain to complete a 4-1 penalty victory.
The record champions PSG, who met last season's Ligue 1 runners-up Marseille after completing a league and cup double, have now lifted this trophy for the twelfth time in the last 13 seasons.
