PSG has now won the season-opening trophy on 14 separate occasions.
Paris Saint-Germain needed a stoppage-time equaliser followed by a successful penalty shootout to get past their arch-rivals in Kuwait and secure a record-extending fourth consecutive French Super Cup title.
The Champions League holders seemed to be coasting towards a straightforward win in the match featuring the Ligue 1 winners and the French Cup holders after the French winger found the scoring early on.
Yet, Marseille fired two times in the closing moments to seize a shock lead. Initially, the English forward converted from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own goal.
In a remarkable twist of events, Goncalo Ramos grabbed a vital leveler in the final seconds to force the match into a deciding shootout. PSG goalkeeper Lucas Chevalier then stood as the hero, stopping decisive attempts from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, Nuno Mendes, and Desire Doue all converted with composure for PSG to complete a 4-1 shootout win.
Now 14-time winners PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after completing a domestic double, have now won this competition for the 12th time in the last 13 seasons.