PSG has now claimed the prestigious trophy on 14 separate times.
Paris Saint-Germain needed a stoppage-time equaliser followed by a perfect penalty shootout to get past Marseille in Kuwait and secure a fourth straight French Super Cup title.
The European champions seemed to be sailing towards a comfortable triumph in the showdown between the Ligue 1 champions and the French Cup holders after the French winger found the scoring in the opening stages.
However, Marseille struck two times in the closing moments to seize a shock advantage. First, Mason Greenwood scored from the penalty spot, before Willian Pacho inadvertently directed the ball into his own net for an own goal.
In a breathtaking turn of events, Goncalo Ramos grabbed a vital equaliser in the dying moments to send the match into a deciding shootout. PSG goalkeeper Chevalier then emerged as the hero, saving decisive attempts from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and the young talent all converted with composure for PSG to complete a convincing penalty victory.
The record winners Paris Saint-Germain, who met last season's Ligue 1 runners-up Olympique de Marseille after completing a league and cup double, have now lifted this trophy for the twelfth time in the last 13 years.
