PSG has now secured the season-opening cup on fourteen different times.
Paris Saint-Germain required a stoppage-time leveler followed by a perfect penalty shootout to overcome Marseille in the Gulf and capture a record-extending fourth consecutive French Super Cup title.
The Champions League holders seemed to be coasting towards a straightforward win in the showdown between the French league champions and the Coupe de France holders after Ousmane Dembele found the scoring in the opening stages.
Yet, Marseille fired twice in the closing moments to take a shock lead. First, Mason Greenwood converted from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own-goal.
In a remarkable twist of fortune, the Portuguese striker snatched a vital equaliser in the final moments to force the contest into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, saving crucial attempts from O'Riley and Traore.
From the spot, Goncalo Ramos, the midfielder, the full-back, and the young talent all scored with composure for PSG to seal a convincing shootout victory.
The record champions PSG, who met last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now lifted this competition for the twelfth time in the last 13 years.