PSG has now secured the prestigious cup on fourteen separate times.
The Parisian giants needed a stoppage-time leveler followed by a perfect spot-kick decider to get past Marseille in the Gulf and capture a record-extending fourth consecutive French Super Cup title.
The European champions seemed to be sailing towards a comfortable win in the showdown featuring the Ligue 1 winners and the Coupe de France winners after the French winger found the net in the opening stages.
However, the southern French side struck twice late to seize a shock advantage. First, the English forward converted from the penalty spot, before the defender inadvertently turned the ball into his own net for an own-goal.
In a breathtaking twist of fortune, Goncalo Ramos grabbed a vital leveler in the final seconds to force the contest into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the key figure, saving crucial attempts from Matt O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, Nuno Mendes, and the young talent all scored successfully for Paris Saint-Germain to seal a convincing penalty victory.
Now 14-time winners PSG, who faced last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now won this trophy for the twelfth time in the past thirteen seasons.
