The Parisian club has now secured the prestigious cup on fourteen separate times.
Paris Saint-Germain required a stoppage-time leveler followed by a successful penalty shootout to overcome their arch-rivals in the Gulf and capture a record-extending fourth consecutive Trophee des Champions title.
The European champions seemed to be coasting towards a straightforward win in the match featuring 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 surprise advantage. First, Mason Greenwood scored from the penalty spot, before Willian Pacho inadvertently directed the ball into his own net for an own-goal.
In a remarkable twist of events, the Portuguese striker snatched a vital equaliser in the dying moments to send the contest into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then stood as the hero, saving decisive attempts from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all converted successfully for PSG to complete a 4-1 shootout win.
Now 14-time winners PSG, who met last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now won this competition for the 12th time in the last 13 seasons.