PSG has now claimed the prestigious cup on 14 separate times.
The Parisian giants required a stoppage-time leveler followed by a successful penalty shootout to overcome their arch-rivals in the Gulf and capture a fourth straight Trophee des Champions title.
The European champions appeared to be coasting towards a comfortable win in the showdown between the Ligue 1 champions and the French Cup winners after the French winger opened the scoring early on.
Yet, the southern French side struck twice late to seize a shock lead. First, the English forward scored from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own-goal.
In a breathtaking turn of events, the Portuguese striker grabbed a vital equaliser in the dying seconds to send the match into a deciding shootout. PSG goalkeeper Chevalier then stood as the hero, saving crucial kicks from O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, Nuno Mendes, and Desire Doue all converted successfully for Paris Saint-Germain to complete a 4-1 penalty victory.
The record champions PSG, who faced last season's Ligue 1 runners-up Marseille after achieving a domestic double, have now lifted this trophy for the 12th time in the past thirteen seasons.
