PSG has now won the prestigious trophy on 14 separate times.
Paris Saint-Germain needed 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 appeared to be coasting towards a comfortable win in the showdown featuring the French league champions and the French Cup winners after the French winger found the net early on.
However, the southern French side struck twice in the closing moments to seize a shock advantage. First, the English forward converted from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own goal.
In a breathtaking turn of fortune, the Portuguese striker grabbed a crucial leveler in the final moments to force the contest into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the hero, stopping decisive kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, the full-back, and the young talent all converted with composure for Paris Saint-Germain to seal a 4-1 penalty win.
The record champions PSG, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a league and cup double, have now lifted this trophy for the twelfth time in the past 13 seasons.
