PSG has now secured the prestigious trophy on 14 different times.
The Parisian giants required a dramatic leveler followed by a perfect spot-kick decider to overcome their arch-rivals in the Gulf and secure a record-extending fourth consecutive Trophee des Champions title.
The Champions League holders appeared to be sailing towards a straightforward win in the showdown between the Ligue 1 winners and the Coupe de France holders after Ousmane Dembele found the scoring early on.
Yet, Marseille struck two times in the closing moments to seize a shock advantage. Initially, Mason Greenwood scored from the spot-kick, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a breathtaking turn of fortune, Goncalo Ramos grabbed a crucial leveler in the final moments to send the contest into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the hero, saving crucial kicks from O'Riley and Traore.
In the shootout, Ramos, Vitinha, the full-back, and Desire Doue all converted successfully for PSG to seal a 4-1 penalty victory.
The record champions PSG, who faced last season's Ligue 1 runners-up Olympique de Marseille after completing a league and cup double, have now lifted this competition for the 12th time in the past 13 years.