PSG has now won the season-opening cup on 14 different times.
The Parisian giants required a dramatic leveler followed by a successful spot-kick decider to get past Marseille in Kuwait and secure a fourth straight French Super Cup title.
The Champions League holders appeared to be coasting towards a comfortable triumph in the match featuring the Ligue 1 champions and the French Cup winners after Ousmane Dembele opened the net early on.
However, the southern French side fired two times in the closing moments to take a surprise advantage. Initially, the English forward converted from the spot-kick, before Willian Pacho inadvertently directed the ball into his own net for an own-goal.
In a breathtaking twist of fortune, Goncalo Ramos grabbed a vital equaliser in the dying seconds to send the match into a penalty shootout. PSG goalkeeper Chevalier then emerged as the key figure, saving crucial kicks from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all scored successfully for PSG to seal a convincing shootout win.
Now 14-time 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 past 13 seasons.
