PSG has now secured the prestigious trophy on 14 separate times.
Paris Saint-Germain needed a stoppage-time equaliser followed by a successful spot-kick decider to overcome their arch-rivals in Kuwait and capture a fourth straight French Super Cup victory.
The European champions appeared to be coasting towards a comfortable triumph in the showdown featuring the Ligue 1 champions and the French Cup holders after Ousmane Dembele opened the net in the opening stages.
However, the southern French side struck two times late to seize a surprise lead. First, Mason Greenwood scored from the spot-kick, 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 final seconds to force the contest into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the key figure, stopping crucial attempts from Matt 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 victory.
Now 14-time champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Marseille after achieving a domestic double, have now won this trophy for the twelfth time in the past 13 years.
