PSG has now claimed the season-opening cup on 14 separate times.
The Parisian giants needed a stoppage-time leveler followed by a successful penalty shootout to overcome Marseille in Kuwait and secure a fourth straight French Super Cup victory.
The Champions League holders appeared to be coasting towards a comfortable triumph in the match featuring the French league winners and the French Cup winners after Ousmane Dembele opened the scoring in the opening stages.
Yet, the southern French side fired twice late to seize a surprise 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 remarkable turn of fortune, Goncalo Ramos snatched a vital leveler in the dying seconds to force the match into a deciding shootout. PSG goalkeeper Lucas Chevalier then emerged as the hero, saving crucial attempts from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and the young talent all scored with composure for PSG to complete a 4-1 penalty victory.
The record winners Paris Saint-Germain, 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 past 13 seasons.
