A first-half penalty miss from Diego proved costly as the Frenchman's second-half header sees the capital club move to the league summit at the expense of Marseille
A second-half header from Kevin Gameiro was all that separated the two sides, with the visitors working hard to stifle Les Parisiens' rhythm throughout. The recently-promoted side had the opportunity to take the lead from the spot late in the first-half, but a brilliant Salvatore Sirigu save denied Diego from 12 yards out.
The hosts opened the match in unconvincing fashion, with Christopher Glombard twice allowed to cut inside from his left flank. His first venture saw the ball eventually cleared by PSG's congested defence, while the second forced Kossi Agassa to parry the Frenchman's effort away from danger.
Maxwell, shifted to a midfield role for the night, should have opened the scoring for his side after being put through by a delicate through ball from Zlatan Ibrahimovic. The striker failed to put power behind his strike however, and Agassa collected calmly.
Carlo Ancelotti's charges grew in confidence as the first-half wore on, dominating possession but failing to find penetration through the middle of the field. The central midfield duo of Alex and Maxwell often resorted to long balls in an attempt to break forward, restricting Les Parisiens to long-range efforts.
And it was a lofted ball that presented Ibrahimovic with the chance to put his side ahead, after Silva found his former Milan team-mate with a well-weighted pass. The Swede was unable to direct his volley on target however, firing wide of goal from a tight angle.
Gameiro came within inches of finding the breakthrough minutes later, after Nene had put the Frenchman through with a classy backheel. The forward could only direct his strike straight at Gassa, with the deflection cleared off the line by Anthony Weber.
Reims were handed a glorious chance to take a lead into the half-time break, with the referee awarding the visitors a penalty following Gregory van der Wiel's handball in the area. Diego stepped up to the spot, but a brilliant save from Sirigu kept the sides level.
Both sides ramped up the pressure with the interval looming, but failed to find a breakthrough in the closing stages. Alex failed to tap in a curling free kick with only the keeper to beat, before Mamadou Sakho put his body on the line at the other end to deny Glombard.
The second-half picked up largely where the first left off, with a dynamic showing from the visitors stemming PSG's rhythm. The hosts were largely restricted to aerial attacks, with Sakho making a mess of a header he should have converted minutes after the break.
Blaise Matuidi then found himself in acres of space in the area following a poor corner clearance from the visitors, but the midfielder could only direct his scrappy effort against the crossbar. The Frenchman then saw a drilled effort deflected by his own team-mate, when the ball appeared to be heading for goal.
The capital club were at last rewarded for their dominance in the 65th minute, when Gameiro latched on to a Maxwell delivery from six yards out. The Frenchman's powerful header left Agassa helpless, and handed his side the lead they and been probing for.
The hosts continued to push for a second in the closing stages, but lacked the final pass to forge opportunities of note.
Ibrahimovic and Menez both had opportunities to put the tie to bed in the final exchanges, but both failed to beat Agasse from narrow angles. Julien Toudic then saw a scissor-kick fly just over at the other end, as he came close to a superb equaliser, but the home side stood firm to hold on for the win.
Victory sees Ancelotti's side provisionally move into top spot, level on 19 points with Marseille, who travel to Troyes on Sunday evening.