PSG has now secured the prestigious cup on fourteen separate times.
Paris Saint-Germain needed a stoppage-time leveler followed by a perfect penalty shootout to get past their arch-rivals in the Gulf and secure a fourth straight Trophee des Champions victory.
The Champions League holders appeared to be coasting towards a comfortable triumph in the showdown between the French league winners and the French Cup winners after the French winger opened the net early on.
However, Marseille struck two times late to take a shock lead. Initially, the English forward scored from the spot-kick, before the defender unfortunately turned the ball into his own net for an own goal.
In a remarkable twist of fortune, Goncalo Ramos snatched a vital equaliser in the dying moments to force the contest into a penalty shootout. PSG goalkeeper Chevalier then emerged as the hero, stopping decisive attempts from O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, Nuno Mendes, and the young talent all converted successfully for PSG to complete a convincing penalty victory.
Now 14-time winners Paris Saint-Germain, who met last season's Ligue 1 runners-up Marseille after achieving a league and cup double, have now won this competition for the twelfth time in the last 13 seasons.
