The Parisian club has now claimed the prestigious cup on fourteen different times.
Paris Saint-Germain needed a dramatic equaliser followed by a perfect spot-kick decider to overcome their arch-rivals in Kuwait and secure a fourth straight French Super Cup victory.
The Champions League holders appeared to be coasting towards a comfortable triumph in the showdown featuring the Ligue 1 winners and the French Cup holders after the French winger found the scoring early on.
Yet, Marseille struck two times late to seize a shock lead. Initially, Mason Greenwood converted from the penalty spot, before the defender inadvertently turned the ball into his own net for an own goal.
In a breathtaking turn of fortune, Goncalo Ramos snatched a vital equaliser in the final seconds to force the match into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, saving decisive attempts from O'Riley and Traore.
From the spot, Ramos, Vitinha, the full-back, and the young talent all scored successfully for Paris Saint-Germain to complete a 4-1 shootout win.
Now 14-time winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after achieving a domestic double, have now won this competition for the twelfth time in the past thirteen years.
