Kylian Mbappe registered his seventh goal in four games with a delightful chipped finish over Dijon goalkeeper Alfred Gomis after 19 minutes.
Mounir Chouiar deservedly levelled for Stephane Jobard's strugglers deep into first-half stoppage time.
Jhonder Cadiz then completed the comeback two minutes after the restart.
Mauro Icardi blazed over from close range and Edinson Cavani dragged a shot narrowly wide as PSG failed to force an equaliser.
The shock result sees Dijon, who only survived in Ligue 1 last season by winning a relegation play-off, climb two places to 18th.
PSG, who had won six straight games and scored 17 goals in their last four, lost just five games on their way to winning the 2018-19 title, but Thomas Tuchel's side have already been beaten three times in the opening 12 games this term.
Unable to establish an 11-point lead on Friday, PSG's closest challengers Nantes can reduce the gap at the top to five points with victory over Bordeaux on Sunday.
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