PSG has now secured the season-opening trophy on fourteen different occasions.
Paris Saint-Germain required a stoppage-time equaliser followed by a successful spot-kick decider to overcome Marseille in the Gulf and capture a record-extending fourth consecutive French Super Cup victory.
The European champions appeared to be coasting towards a comfortable win in the match featuring the French league champions and the Coupe de France winners after the French winger opened the net early on.
Yet, the southern French side struck twice in the closing moments to take a shock lead. First, the English forward scored from the spot-kick, before Willian Pacho unfortunately directed the ball into his own net for an own goal.
In a remarkable twist of events, Goncalo Ramos grabbed a vital equaliser in the dying seconds to send the contest into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, saving decisive kicks from Matt O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all converted with composure for PSG to seal a convincing penalty win.
The record winners PSG, who met last season's Ligue 1 runners-up Marseille after completing a domestic double, have now won this trophy for the 12th time in the last 13 years.