The Parisian club has now claimed the season-opening cup on 14 different times.
The Parisian giants needed a stoppage-time leveler followed by a successful penalty shootout to get past their arch-rivals in the Gulf and secure a record-extending fourth consecutive Trophee des Champions victory.
The Champions League holders appeared to be coasting towards a comfortable triumph in the showdown between the French league champions and the Coupe de France winners after the French winger opened the net early on.
Yet, Marseille struck twice in the closing moments to seize a shock advantage. First, the English forward converted from the spot-kick, before Willian Pacho inadvertently turned 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 force the match into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the key figure, saving decisive kicks from Matt O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, Nuno Mendes, and the young talent all converted with composure for Paris Saint-Germain to complete a 4-1 shootout win.
The record winners Paris Saint-Germain, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a league and cup double, have now won this competition for the twelfth time in the past thirteen seasons.
