A team including Lionel Messi and Kylian Mbappe drew the ire of the fans inside the Parc des Princes at the end of both halves as PSG fell to their fifth defeat in their last nine games across all competitions courtesy of goals from Karl Toko Ekambi and Arnaud Kalimuendo either side of half time.
While that run has included exits from the Coupe de France and the Champions League, the latest loss is likely to be less costly, with the defending champions still nine points clear at the top of the Ligue 1 table.
However, the result will pile more pressure on the shoulders of underfire manager Christophe Galtier, as well as raising renewed questions over the futures of Messi and Mbappe.
Rennes arrived in the capital with reason to believe that they could end PSG's 35-match unbeaten home run in the league, given that they had won three of their previous six meetings with the champions, including the reverse fixture, while manager Bruno Genesio has more wins over PSG in Ligue 1 than anyone else since the Qatari takeover of the club.
The hosts were nonetheless in command for the vast majority of the opening 45 minutes, with the best chances falling the way of Mbappe and Messi.
However, a mixture of slightly wayward finishing and a brilliant performance from Steve Mandanda in the Rennes goal kept the star duo at bay, and there was a sting in the tail of the first half too as Rennes broke the deadlock just before the interval.
Benjamin Bourigeaud's long pass forward from defence was enough to take the entire PSG defence out of the game, and Toko Ekambi latched on to it before firing low past Gianluigi Donnarumma for the first Ligue 1 goal of his loan spell.
While that goal came firmly against the run of play, Rennes began the second half in equally clinical fashion to double their advantage just three minutes after the restart as former PSG man Kalimuendo slid home to convert Toko Ekambi's cross.
The hosts pushed for a route back into the match, with Fabian Ruiz, Messi, Marco Verratti, Warren Zaire-Emery and Vitinha all having sights of goal, but their enforced gung-ho approach also opened the door for Rennes counter-attacks and Djed Spence almost inflicted further misery at the other end.
The visitors ultimately did not need a third, though, as they held on for a win which sees them complete the double over PSG, who have now failed to score in both of their games against Rennes this season - the only league matches in which they have drawn a blank.
The win lifts Rennes up to fifth, while Marseille will have the chance to cut PSG's lead to seven points when they face Reims in the late Ligue 1 kickoff.