The Parisian club has now claimed the prestigious cup on fourteen different times.
Paris Saint-Germain required a stoppage-time equaliser followed by a perfect spot-kick decider to overcome Marseille in Kuwait and secure a record-extending fourth consecutive Trophee des Champions victory.
The European champions seemed to be coasting towards a straightforward win in the match featuring the French league champions and the French Cup winners after the French winger found the scoring early on.
However, the southern French side fired twice in the closing moments to take a shock advantage. First, the English forward scored from the spot-kick, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a breathtaking twist of fortune, Goncalo Ramos snatched a vital equaliser in the final seconds to force the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the hero, stopping decisive kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all scored successfully for PSG to seal a convincing shootout victory.
The record champions PSG, who met last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now lifted this competition for the twelfth time in the last thirteen years.
