PSG has now claimed the season-opening trophy on 14 separate times.
Paris Saint-Germain needed a stoppage-time equaliser followed by a successful spot-kick decider to overcome Marseille in the Gulf and capture a fourth straight Trophee des Champions victory.
The Champions League holders appeared to be coasting towards a straightforward win in the match between the Ligue 1 winners and the French Cup winners after the French winger opened the scoring early on.
However, the southern French side fired twice late to seize 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 turn of fortune, Goncalo Ramos snatched a crucial leveler in the final seconds to force the contest into a deciding shootout. PSG goalkeeper Chevalier then stood as the key figure, stopping crucial attempts from O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, the full-back, and the young talent all converted with composure for PSG to seal a 4-1 penalty victory.
The record winners PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a domestic double, have now lifted this trophy for the twelfth time in the past 13 years.
