The Parisian club has now claimed the prestigious trophy on 14 separate times.
Paris Saint-Germain required a dramatic equaliser followed by a perfect spot-kick decider to overcome their arch-rivals in Kuwait and capture a record-extending fourth consecutive French Super Cup victory.
The Champions League holders appeared to be sailing towards a straightforward triumph in the match between the Ligue 1 champions and the French Cup winners after the French winger found the net in the opening stages.
Yet, Marseille fired twice in the closing moments to seize a shock advantage. First, Mason Greenwood converted from the penalty spot, before Willian Pacho inadvertently turned the ball into his own net for an own goal.
In a breathtaking turn of fortune, Goncalo Ramos grabbed a crucial equaliser in the final moments to send the match into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, saving decisive kicks from O'Riley and Traore.
From the spot, Ramos, the midfielder, Nuno Mendes, and the young talent all scored successfully for PSG to complete a 4-1 penalty win.
Now 14-time winners PSG, who met last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now won this competition for the 12th time in the past 13 seasons.
