The Parisian club has now secured the season-opening trophy on 14 separate occasions.
The Parisian giants required a stoppage-time equaliser followed by a successful spot-kick decider to get past 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 showdown featuring the French league champions and the French Cup holders after Ousmane Dembele found the scoring early on.
However, Marseille fired two times late to seize a shock advantage. First, Mason Greenwood converted from the penalty spot, before Willian Pacho unfortunately 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 dying seconds to send the match into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then stood as the hero, saving decisive attempts from Matt O'Riley and Traore.
In the shootout, Ramos, the midfielder, Nuno Mendes, and the young talent all converted successfully for PSG to seal a 4-1 penalty victory.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 second-placed team Olympique de Marseille after completing a league and cup double, have now won this competition for the twelfth time in the last 13 seasons.
