PSG has now won the prestigious cup on 14 different occasions.
The Parisian giants required a stoppage-time leveler followed by a perfect spot-kick decider to overcome their arch-rivals in the Gulf and secure a fourth straight Trophee des Champions title.
The Champions League holders seemed to be sailing towards a straightforward triumph in the showdown between the Ligue 1 champions and the French Cup winners after the French winger found the net in the opening stages.
However, Marseille struck two times in the closing moments to take a surprise advantage. First, Mason Greenwood converted from the penalty spot, before Willian Pacho unfortunately turned the ball into his own net for an own-goal.
In a remarkable turn of events, the Portuguese striker grabbed a vital equaliser in the final seconds to force the match into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then stood as the key figure, saving decisive attempts from O'Riley and Traore.
In the shootout, Goncalo Ramos, Vitinha, the full-back, and the young talent all scored successfully for PSG to complete a convincing shootout victory.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Marseille after achieving a domestic double, have now won this competition for the twelfth time in the past thirteen seasons.
