PSG has now claimed the prestigious trophy on 14 different occasions.
The Parisian giants required a dramatic equaliser followed by a successful spot-kick decider to overcome Marseille in the Gulf and capture a record-extending fourth consecutive French Super Cup victory.
The European champions seemed to be sailing towards a straightforward triumph in the showdown between the Ligue 1 champions and the Coupe de France holders after the French winger opened the net in the opening stages.
Yet, the southern French side fired two times late to seize a surprise advantage. First, the English forward scored 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, the Portuguese striker grabbed a vital equaliser in the final seconds to send the match into a penalty shootout. PSG goalkeeper Chevalier then stood as the hero, saving crucial kicks from Matt O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all converted successfully for Paris Saint-Germain to complete a convincing penalty win.
The record champions Paris Saint-Germain, who met 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 last thirteen years.
