The Parisian club has now secured the season-opening trophy on fourteen different times.
Paris Saint-Germain required a stoppage-time equaliser followed by a perfect penalty shootout to get past Marseille in the Gulf and capture a fourth straight French Super Cup title.
The Champions League holders appeared to be sailing towards a straightforward win in the match between the Ligue 1 winners and the French Cup holders after the French winger opened the scoring early on.
Yet, Marseille fired two times in the closing moments to take a shock advantage. Initially, the English forward converted from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a remarkable turn of events, Goncalo Ramos snatched a vital equaliser in the dying moments to send the contest into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, stopping decisive kicks from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, the full-back, and the young talent all scored successfully for Paris Saint-Germain to seal a 4-1 shootout win.
Now 14-time champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now lifted this competition for the twelfth time in the past 13 years.
