The Parisian club has now secured the season-opening cup on 14 different occasions.
Paris Saint-Germain needed a dramatic leveler followed by a perfect penalty shootout to overcome their arch-rivals in the Gulf and capture a record-extending fourth consecutive French Super Cup title.
The European champions appeared to be coasting towards a comfortable triumph in the showdown featuring the French league winners and the Coupe de France holders after the French winger found the net in the opening stages.
However, Marseille struck twice in the closing moments to seize a surprise lead. First, the English forward converted from the spot-kick, before the defender 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 moments to force the match into a penalty shootout. PSG goalkeeper Lucas Chevalier then emerged as the key figure, saving crucial attempts from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and Desire Doue all scored with composure for Paris Saint-Germain to seal a 4-1 shootout victory.
The record winners PSG, who faced last season's Ligue 1 runners-up Olympique de Marseille after completing a league and cup double, have now lifted this competition for the 12th time in the past thirteen years.