PSG has now secured the prestigious cup 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 record-extending fourth consecutive French Super Cup title.
The Champions League holders appeared to be sailing towards a straightforward triumph in the match between the Ligue 1 winners and the Coupe de France winners after Ousmane Dembele opened the scoring in the opening stages.
Yet, the southern French side fired two times in the closing moments to take a shock advantage. First, the English forward converted from the penalty spot, before Willian Pacho unfortunately turned the ball into his own net for an own-goal.
In a remarkable turn of fortune, the Portuguese striker snatched a vital leveler in the final moments to force the match into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, saving decisive attempts from Matt O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, Nuno Mendes, and Desire Doue all converted with composure for PSG to seal a 4-1 penalty victory.
The record champions PSG, who met last season's Ligue 1 runners-up Marseille after achieving a league and cup double, have now won this competition for the 12th time in the past thirteen seasons.
