PSG has now claimed the prestigious cup on fourteen separate times.
The Parisian giants required a dramatic equaliser followed by a successful spot-kick decider to get past Marseille in Kuwait and capture a fourth straight French Super Cup title.
The European champions seemed to be coasting towards a straightforward triumph in the match between the Ligue 1 champions and the Coupe de France holders after Ousmane Dembele opened the scoring early on.
Yet, the southern French side struck twice in the closing moments to seize a shock advantage. First, the English forward scored from the penalty spot, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a remarkable twist of events, Goncalo Ramos snatched a vital equaliser in the dying moments to force the contest into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, stopping crucial kicks from O'Riley and Traore.
In the shootout, Ramos, Vitinha, the full-back, and Desire Doue all converted with composure for PSG to complete a convincing penalty win.
The record champions PSG, who faced last season's Ligue 1 runners-up Olympique de Marseille after achieving a league and cup double, have now won this competition for the twelfth time in the last thirteen seasons.
