PSG has now secured the prestigious cup on 14 separate occasions.
The Parisian giants required a stoppage-time equaliser followed by a perfect spot-kick decider to get past Marseille in the Gulf and capture a record-extending fourth consecutive French Super Cup victory.
The European champions seemed to be coasting towards a comfortable triumph in the showdown between the Ligue 1 champions and the French Cup holders after the French winger found the scoring early on.
Yet, Marseille struck twice late to seize a shock advantage. First, Mason Greenwood converted from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a breathtaking turn of fortune, the Portuguese striker grabbed a crucial leveler in the final seconds to force the contest into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the hero, saving decisive kicks from Matt O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all converted with composure for PSG to complete a convincing shootout victory.
Now 14-time champions PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now lifted this competition for the twelfth time in the last thirteen seasons.
