The Parisian club has now won the prestigious trophy on 14 separate times.
Paris Saint-Germain needed a stoppage-time equaliser followed by a perfect spot-kick decider to overcome Marseille in the Gulf and secure a record-extending fourth consecutive French Super Cup victory.
The European champions appeared to be coasting towards a straightforward win in the showdown between the French league winners and the Coupe de France holders after the French winger opened the net early on.
Yet, the southern French side fired twice late to take a shock lead. Initially, the English forward converted from the penalty spot, before Willian Pacho inadvertently directed the ball into his own net for an own-goal.
In a remarkable twist of fortune, Goncalo Ramos grabbed a vital equaliser in the dying seconds to force the match into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the hero, stopping decisive kicks from Matt O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, the full-back, and the young talent all scored with composure for Paris Saint-Germain to seal a convincing penalty victory.
Now 14-time champions PSG, who faced last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now won this trophy for the twelfth time in the last thirteen seasons.
