PSG has now secured the season-opening trophy on 14 separate times.
The Parisian giants needed a dramatic equaliser followed by a perfect penalty shootout to overcome Marseille in the Gulf and secure a fourth straight French Super Cup victory.
The Champions League holders seemed to be sailing towards a comfortable win in the showdown between the Ligue 1 winners and the French Cup holders after Ousmane Dembele opened the scoring in the opening stages.
However, the southern French side struck twice late to take a surprise advantage. First, the English forward scored from the penalty spot, before the defender unfortunately turned the ball into his own net for an own-goal.
In a breathtaking turn of fortune, Goncalo Ramos snatched a crucial equaliser in the final seconds to force the contest into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the hero, saving decisive attempts from Matt O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all converted with composure for PSG to seal a convincing penalty win.
The record champions Paris Saint-Germain, who met last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now won this trophy for the 12th time in the last 13 seasons.
