PSG has now claimed the season-opening cup on 14 separate times.
The Parisian giants needed a stoppage-time equaliser followed by a perfect spot-kick decider to get past their arch-rivals in the Gulf and capture a fourth straight French Super Cup victory.
The Champions League holders appeared to be coasting towards a comfortable win in the match between the Ligue 1 winners and the French Cup holders after the French winger found the scoring in the opening stages.
However, the southern French side struck two times late to seize a shock advantage. First, Mason Greenwood scored from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own goal.
In a remarkable turn of events, Goncalo Ramos grabbed a vital equaliser in the final moments to force the match into a penalty shootout. PSG goalkeeper Chevalier then stood as the key figure, stopping crucial kicks from Matt O'Riley and Traore.
From the spot, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all scored successfully for PSG to complete a convincing shootout victory.
Now 14-time winners 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 last 13 years.
