PSG has now claimed the season-opening cup on fourteen different times.
The Parisian giants needed a dramatic equaliser followed by a successful penalty shootout to overcome their arch-rivals in Kuwait and capture a fourth straight French Super Cup title.
The Champions League holders seemed to be coasting towards a straightforward triumph in the showdown featuring the French league champions and the Coupe de France holders after the French winger opened the scoring early on.
However, Marseille struck twice in the closing moments to seize a shock lead. First, Mason Greenwood converted from the spot-kick, before the defender unfortunately directed the ball into his own net for an own-goal.
In a remarkable turn of events, Goncalo Ramos snatched a vital equaliser in the final seconds to send the contest into a deciding shootout. PSG goalkeeper Chevalier then emerged as the key figure, saving decisive kicks from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and the young talent all converted successfully for Paris Saint-Germain to complete a 4-1 shootout win.
The record champions Paris Saint-Germain, who met last season's Ligue 1 runners-up Olympique de Marseille after completing a domestic double, have now lifted this trophy for the 12th time in the past 13 seasons.
