PSG has now won the prestigious trophy on 14 different occasions.
Paris Saint-Germain required a dramatic leveler followed by a successful penalty shootout to get past Marseille in the Gulf and capture a fourth straight French Super Cup victory.
The European champions seemed to be coasting towards a comfortable triumph in the match featuring the Ligue 1 winners and the Coupe de France winners after Ousmane Dembele found the scoring early on.
Yet, the southern French side fired two times late to take a surprise advantage. Initially, Mason Greenwood 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 fortune, Goncalo Ramos grabbed a vital equaliser in the final seconds to send the match into a deciding shootout. PSG goalkeeper Chevalier then emerged as the hero, stopping decisive attempts from O'Riley and Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all scored successfully for PSG to seal a 4-1 shootout victory.
The record winners 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 12th time in the last 13 years.
