The Parisian club has now won the prestigious trophy on 14 different occasions.
The Parisian giants needed a stoppage-time equaliser followed by a perfect spot-kick decider to overcome Marseille in the Gulf and capture a record-extending fourth consecutive French Super Cup title.
The European champions appeared to be coasting towards a straightforward triumph in the match featuring the French league winners and the Coupe de France holders after the French winger opened the net early on.
However, the southern French side fired twice in the closing moments to seize a shock lead. First, the English forward scored from the spot-kick, before Willian Pacho inadvertently directed the ball into his own net for an own-goal.
In a remarkable turn of events, the Portuguese striker grabbed a crucial leveler in the dying moments to force the contest into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the hero, stopping decisive kicks from O'Riley and Traore.
In the shootout, Goncalo Ramos, the midfielder, the full-back, and the young talent all scored successfully for PSG to complete a 4-1 shootout victory.
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 won this competition for the twelfth time in the past thirteen seasons.
