PSG has now won the season-opening trophy on fourteen separate times.
Paris Saint-Germain required a dramatic leveler followed by a perfect penalty shootout to overcome their arch-rivals in the Gulf and capture a fourth straight Trophee des Champions title.
The European champions seemed to be coasting towards a comfortable win in the match between the Ligue 1 winners and the Coupe de France holders after the French winger opened the net in the opening stages.
Yet, Marseille struck two times late to take a shock advantage. Initially, the English forward scored from the penalty spot, before the defender unfortunately directed the ball into his own net for an own goal.
In a breathtaking twist of fortune, the Portuguese striker snatched a vital equaliser in the final moments to send the match into a deciding shootout. PSG goalkeeper Lucas Chevalier then stood as the key figure, stopping decisive kicks from O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, Nuno Mendes, and the young talent all converted with composure for PSG to seal a 4-1 penalty victory.
The record winners Paris Saint-Germain, who met last season's Ligue 1 runners-up Marseille after completing a domestic double, have now won this trophy for the 12th time in the last 13 seasons.