PSG has now won the prestigious cup on 14 separate times.
The Parisian giants required a dramatic equaliser followed by a perfect spot-kick decider to overcome their arch-rivals in the Gulf and capture a fourth straight French Super Cup title.
The Champions League holders appeared to be coasting towards a comfortable win in the showdown between the Ligue 1 winners and the French Cup holders after the French winger opened the net in the opening stages.
However, Marseille struck twice late to seize a shock advantage. First, Mason Greenwood converted from the penalty spot, before the defender inadvertently turned the ball into his own net for an own goal.
In a remarkable twist of events, the Portuguese striker snatched a vital leveler in the dying moments to send the contest into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the hero, saving decisive attempts from Matt O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all scored with composure for PSG to complete a 4-1 penalty victory.
The record champions PSG, who faced last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now won this trophy for the twelfth time in the last thirteen seasons.
