The Parisian club has now claimed the prestigious cup on 14 different times.
Paris Saint-Germain required a stoppage-time leveler followed by a perfect spot-kick decider to overcome their arch-rivals in the Gulf and capture a fourth straight Trophee des Champions victory.
The European champions appeared to be sailing towards a comfortable triumph in the showdown featuring the Ligue 1 champions and the French Cup winners after the French winger found the net in the opening stages.
However, Marseille fired twice in the closing moments to take a surprise lead. First, Mason Greenwood scored from the penalty spot, before Willian Pacho inadvertently turned the ball into his own net for an own goal.
In a breathtaking twist of fortune, Goncalo Ramos snatched a vital equaliser in the final moments to force the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the key figure, stopping crucial kicks from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored with composure for Paris Saint-Germain to complete a convincing shootout win.
Now 14-time champions PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a league and cup double, have now lifted this competition for the 12th time in the last thirteen seasons.
