PSG has now secured the prestigious cup on fourteen different occasions.
Paris Saint-Germain needed a dramatic leveler followed by a perfect spot-kick decider to overcome Marseille in Kuwait and capture a fourth straight Trophee des Champions title.
The European champions appeared to be sailing towards a comfortable triumph in the showdown between the French league champions and the French Cup winners after the French winger found the scoring in the opening stages.
Yet, the southern French side fired twice late to seize a surprise advantage. First, the English forward scored from the spot-kick, before the defender inadvertently directed the ball into his own net for an own-goal.
In a remarkable twist of fortune, the Portuguese striker grabbed a vital equaliser in the dying moments to force the match into a penalty shootout. PSG goalkeeper Chevalier then stood as the hero, stopping crucial kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, Nuno Mendes, and the young talent all converted successfully for Paris Saint-Germain to seal a 4-1 penalty victory.
The record winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a league and cup double, have now lifted this trophy for the twelfth time in the last 13 years.