In a thrilling seven goal encounter at Stade du Hainaut, les Parisiens came out on top against a spirited Valenciennes side to go top of the table, for 24 hours at least.
Vincent Aboubakar put the hosts ahead after eight minutes with a deflected strike, before Remi Gomis doubled the lead three minutes later after some lax defending.
A Parisien comeback was expected and it didn't disappoint either. Nene reduced the deficit after 15 minutes with his fourth goal against Valenciennes in four matches, before Maxwell and Blaise Matuidi both notched their first goals for the club just before half-time.
Jeremy Menez made it 4-2 in the second half, before a fine Renaud Cohade free kick ensured a tense finish in a thrilling encounter.
Carlo Ancelotti opted to continue deploying Zoumana Camara in central defence alongside Alex, despite club captain Mamadou Sakho returning from a suspension. Jeremy Menez led the attacking line, leaving forwards Kevin Gameiro and Guillaume Hoarau on the bench. Meanwhile, the hosts were boosted with the return of Carlos Sanchez from a nine-game suspension.
With Montpellier dropping points in midweek, the onus was on the capital club to defeat Valenciennes and return provisionally to the top of the table. Though within eight minutes, it would be Daniel Sanchez's men to take a shock lead.
After an edgy beginning to proceedings at Stade du Hainaut, a lofted ball from Rudy Mater found Aboubakar who displayed an incredible piece of control to turn the ball away from his marker and fire an effort towards Salvatore Sirigu, via a heavy deflection off an unsuspecting Alex for 1-0.
If the goal came as anything as a shock to the home faithful, the second would send them into delirium. The visitors' failed to negotiate a sustained Valenciennes attack. Aboubakar again was the architect, directing a powerful strike towards Sirigu after a wonderful series of dribbles. With the Italian parrying the loose ball back into the danger zone Gomis was left to tap into an empty net for 2-0 after 11 minutes.
PSG's shell-shocked unit issued a response, and adjusting their tempo accordingly. It worked, as les Parisiens alved the deficit four minutes later after sustained pressure. A poor clearance from Mater saw Menez retain possession of the ball and thread a ball towards Nene. The Brazilian in turn, fired a low shot past Penneteau for his 18th league strike of the season.
Valenciennes kept up the charge despite the setback, and were unlucky not to have gone further ahead, after Gael Danic's through ball was agonisingly cut out at the last minute by Alex. At the other end, Javier Pastore was denied a strong penalty call by referee Fredy Fautrel after a rash challenge from Nicolas Isimat-Mirin.
Ancelotti's side grew in stature as the first half progressed, with Daniel Sanchez's men unable to keep up with the visitors' fine counter-attacking movement. Four minutes before half-time, the equaliser arrived in typical PSG fashion.
Affter a distinctly high-octane surge forward from Jallet, it was Nene who clipped a neat ball towards Maxwell, arriving on the overlap. The former Barcelona defender, at an acute angle, slamming a low shot under Penneteau for his first goal in French football.
It got even better for les Parisiens, as on the stroke of half-time, they superbly completed the comeback. A fine ball over the Valenciennes from Pastore deep in midfield, picked out Matuidi who kept his calm to slide the ball past the goalkeeper for 3-2 in what became an important 45 minutes in the title race.
The second period began in equally end-to-end fashion as the first. Another through-ball carved open the Valenciennes back-line before Menez was forced wide with a fine save from Penneteau. At the other end, almost immediately, Foued Kadir was denied by Sirigu as both sides stepped up respective efforts.
Nevertheless, it was PSG who struck a decisive blow just before the hour. A fine move from Nene located Menez who swiftly directed the ball into the net and put clear daylight between the two sides as the game ultimately swung in the balance of the title challengers.
For all of Valenciennes' enterprising efforts, they wilted away alarmingly but still managed to grab a late goal. A superb free-kick from Cohade past the clutches of Sirigu and off the post ensured a tense finish, which PSG saw out.
Paris Saint-Germain go top of Ligue 1 on goals scored, with Montpellier encountering Stade Rennes in their week 36 clash on Monday. Carlo Ancelotti's side host les Rouge et Noir in their final home game, as Valenciennes play Brest in week 37.