PSG has now claimed the prestigious cup on fourteen separate times.
The Parisian giants needed a dramatic leveler followed by a perfect penalty shootout to get past their arch-rivals in the Gulf and secure a record-extending fourth consecutive Trophee des Champions title.
The Champions League holders seemed to be sailing towards a comfortable triumph in the showdown between the French league winners and the French Cup holders after Ousmane Dembele opened the net early on.
Yet, Marseille struck two times late to seize a shock advantage. First, the English forward converted from the spot-kick, before the defender unfortunately turned the ball into his own net for an own goal.
In a breathtaking twist of fortune, the Portuguese striker grabbed a vital leveler in the dying seconds to send the match into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the hero, stopping crucial kicks from Matt O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, the full-back, and Desire Doue all scored with composure for PSG to seal a convincing shootout win.
Now 14-time winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now lifted this competition for the 12th time in the last thirteen years.
