The Parisian club has now secured the season-opening trophy on fourteen separate times.
The Parisian giants needed a dramatic leveler followed by a perfect spot-kick decider 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 sailing towards a straightforward win in the showdown between the French league winners and the French Cup holders after the French winger opened the net in the opening stages.
Yet, the southern French side fired twice late to take a shock advantage. First, Mason Greenwood converted from the spot-kick, before the defender unfortunately directed the ball into his own net for an own-goal.
In a remarkable twist of fortune, Goncalo Ramos grabbed a crucial leveler in the dying seconds to force the contest into a penalty shootout. PSG goalkeeper Lucas Chevalier then stood as the hero, stopping crucial kicks from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all scored successfully for PSG to complete a 4-1 shootout win.
The record champions PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now won this trophy for the 12th time in the last thirteen years.