PSG has now secured the season-opening trophy on fourteen separate occasions.
The Parisian giants needed a dramatic leveler followed by a perfect penalty shootout to overcome their arch-rivals in Kuwait and secure a fourth straight French Super Cup title.
The European champions seemed to be sailing towards a comfortable win in the match featuring the French league winners and the French Cup holders after Ousmane Dembele opened the net in the opening stages.
However, Marseille struck two times in the closing moments to seize a surprise advantage. Initially, the English forward scored from the spot-kick, before Willian Pacho unfortunately directed the ball into his own net for an own goal.
In a breathtaking turn of fortune, the Portuguese striker snatched a vital leveler in the final seconds to send the match into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, saving decisive attempts from Matt O'Riley and Traore.
From the spot, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all scored with composure for Paris Saint-Germain to complete a 4-1 shootout win.
The record winners PSG, who met last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now lifted this competition for the twelfth time in the last thirteen seasons.
