PSG has now secured the season-opening cup on fourteen separate occasions.
The Parisian giants needed a dramatic equaliser followed by a perfect spot-kick decider to get past Marseille in Kuwait and capture a fourth straight French Super Cup victory.
The Champions League holders appeared to be sailing towards a comfortable win in the showdown between the Ligue 1 winners and the Coupe de France winners after the French winger found the scoring early on.
However, the southern French side struck two times late to take a shock advantage. First, Mason Greenwood converted from the spot-kick, before the defender unfortunately turned the ball into his own net for an own goal.
In a remarkable twist of fortune, the Portuguese striker snatched a crucial equaliser in the dying moments to force the match into a penalty shootout. PSG goalkeeper Chevalier then stood as the key figure, stopping crucial kicks from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and the young talent all scored successfully for PSG to seal a convincing penalty victory.
The record winners PSG, who faced last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now lifted this competition for the 12th time in the last thirteen years.
