The Parisian club has now won the season-opening trophy on 14 separate times.
The Parisian giants needed a stoppage-time equaliser followed by a successful penalty shootout to get past Marseille in Kuwait and secure a fourth straight Trophee des Champions title.
The European champions seemed to be coasting towards a straightforward triumph in the match between the Ligue 1 champions and the French Cup winners after the French winger opened the net in the opening stages.
Yet, the southern French side fired two times in the closing moments to take a surprise advantage. First, Mason Greenwood scored from the penalty spot, before Willian Pacho unfortunately turned the ball into his own net for an own-goal.
In a breathtaking twist of events, the Portuguese striker snatched a vital equaliser in the final moments to force the match into a deciding shootout. PSG goalkeeper Chevalier then emerged as the key figure, stopping decisive attempts from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, the full-back, and the young talent all converted with composure for Paris Saint-Germain to seal a convincing penalty victory.
The record winners Paris Saint-Germain, 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 last 13 years.