PSG has now won the season-opening trophy on fourteen separate times.
Paris Saint-Germain needed a dramatic equaliser followed by a successful spot-kick decider to get past Marseille in Kuwait and capture a record-extending fourth consecutive Trophee des Champions victory.
The Champions League holders seemed to be coasting towards a comfortable triumph in the match between the Ligue 1 champions and the French Cup holders after Ousmane Dembele opened the net in the opening stages.
However, the southern French side fired two times in the closing moments to seize a shock lead. First, Mason Greenwood scored from the penalty spot, before the defender unfortunately turned the ball into his own net for an own goal.
In a breathtaking turn of events, the Portuguese striker snatched a vital equaliser in the dying seconds to send the match into a penalty shootout. PSG goalkeeper Lucas Chevalier then stood as the key figure, saving crucial attempts from O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, Nuno Mendes, and the young talent all scored successfully for PSG to seal a convincing shootout win.
Now 14-time champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now lifted this competition for the 12th time in the past 13 seasons.