PSG has now claimed the season-opening cup on 14 different times.
The Parisian giants needed a dramatic equaliser followed by a perfect spot-kick decider to overcome Marseille in the Gulf and capture a fourth straight French Super Cup victory.
The Champions League holders appeared to be sailing towards a comfortable triumph in the showdown featuring the Ligue 1 champions and the French Cup winners after the French winger opened the net early on.
Yet, Marseille fired two times late to seize a surprise lead. Initially, Mason Greenwood converted from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a remarkable turn of events, Goncalo Ramos snatched a crucial leveler in the final moments to force the contest into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the hero, saving decisive attempts from Matt O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and the young talent all scored with composure for Paris Saint-Germain to seal a convincing penalty victory.
The record winners PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after completing a league and cup double, have now won this competition for the 12th time in the last thirteen seasons.
