The Parisian club has now secured the season-opening trophy on fourteen separate times.
The Parisian giants needed a stoppage-time equaliser followed by a perfect spot-kick decider to overcome Marseille in Kuwait and capture a fourth straight Trophee des Champions victory.
The European champions seemed to be sailing towards a straightforward triumph in the match featuring the Ligue 1 champions and the French Cup holders after the French winger opened the scoring early on.
Yet, the southern French side struck two times in the closing moments to take a shock lead. Initially, the English forward converted from the spot-kick, before Willian Pacho inadvertently directed the ball into his own net for an own-goal.
In a breathtaking twist of events, Goncalo Ramos snatched a crucial leveler in the final moments to force the contest into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the key figure, stopping crucial kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, Nuno Mendes, and the young talent all scored successfully for PSG to seal a 4-1 penalty win.
The record champions Paris Saint-Germain, who met last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now won this competition for the twelfth time in the past thirteen seasons.