The Parisian club has now won the season-opening cup on 14 separate occasions.
Paris Saint-Germain required a dramatic leveler followed by a perfect spot-kick decider to overcome their arch-rivals in the Gulf and secure a fourth straight Trophee des Champions victory.
The Champions League holders seemed to be coasting towards a comfortable triumph in the showdown featuring the Ligue 1 winners and the French Cup holders after the French winger opened the net in the opening stages.
However, Marseille fired twice in the closing moments to seize a shock lead. Initially, Mason Greenwood converted from the spot-kick, before the defender inadvertently directed the ball into his own net for an own goal.
In a breathtaking turn of fortune, the Portuguese striker snatched a crucial leveler in the final seconds to force the contest into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, saving decisive attempts from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and the young talent all scored with composure for PSG to complete a 4-1 shootout victory.
The record winners PSG, who met last season's Ligue 1 runners-up Marseille after completing a domestic double, have now lifted this competition for the 12th time in the last 13 years.
