Valencia were left to rue Sergio Busquets' last-gasp winner as Barcelona prevailed with a dramatic 1-0 victory at Mestalla.
The hosts' former defender Jeremy Mathieu replaced Marc Bartra in the La Blaugrana defence, having been rested for the midweek Champions League trip to APOEL, while Sergio Busquets, Xavi and Neymar all returned to the line-up in favour of Javier Mascherano, Rafinha and Pedro Rodriguez.
Valencia, on the other hand, made two changes from last week's 2-1 defeat to Levante, as Dani Parejo and Sofiane Feghouli came in at the expense of Carles Gil and Pablo Piatti. Los Che also matched Barca with a 4-3-3 formation, switching from their usual 4-4-2.
Purists were initially treated to an open encounter, with Valencia carving out the match's first opening. Rodrigo found space on the left-hand side and drove towards the edge of the box but saw his low strike parried away by Claudio Bravo.
Minutes later, Luis Suarez fluffed a glorious opportunity to break his duck in La Liga after he latched onto Sergio Busquets' defence-splitting through ball but only struck the chest of Diego Alves from point-blank range.
However, the match soon descended into a comedy of histrionics. First, Neymar was fortunate to avoid punishment following his minor headbutt into the cheek of Nicolas Otamendi, although the defender's reaction to the touch was grossly exaggerated.
There was no love lost between the two outfits, with Mathieu, Jordi Alba and Shkodran Mustafi all deliberately picking up yellow cards, while Dani Alves was fortunate to have avoided the referee's book.
With the half coming to a close, Andre Gomes fired a low shot from around 20 yards out just wide of the post, but not before Parejo blazed a half-volleyed attempt over the bar following a failed clearance from Neymar.
The Portuguese could have given Valencia an invaluable lead on the cusp of half-time, had he managed to keep his composure after rounding Bravo in the box, but he only managed to send a finish into the side-netting, as his angles increasingly diminished.
The second half needed some time to warm up, and so it did on the hour mark when Luis Suarez beat Otamendi to a 50-50 near the home side's penalty area, but the Uruguayan got his bearings all wrong and smashed his finish into side-netting.
Los Che hit back from a corner through Mustafi, who shrugged off Mascherano's advanced and laid the ball off for Rodrigo, who subsequently forced Gerard Pique into making a goal-line clearance.
Neymar was next up, as he dragged an attempt from distance a matter of inches wide, before he drilled a low cross into the box for Suarez to tuck away. However, the Uruguayan was incorrectly flagged offside.
Nuno Santo's troops refused to back down in light of Barca's dominance in possession, and they almost caught their visitors out on the counterattack, as Negredo's slide-rule pass found Feghouli in the clear, but the Algerian was denied by Bravo.
Valencia would ultimately rue their misfortune, as Bravo came to Barca's rescue once more. Jose Luis Gaya's cross fell to Negredo in the box, and the striker turned and rifled a shot which the Chilean tipped wide of the post.
Deep in injury time, Otamendi thought he had saved his side a point thanks to his crucial intervention on Lionel Messi, but with seconds remaining, Busquets flung himself onto the rebound from Neymar's saved header to earn Barca a famous win.
The match ended on a sour note, however as Messi was hit on the back of the head by an object thrown by a member of the crowd during his teammate’s goal celebration and needed treatment.
Valencia 0-1 Barcelona
Busquets 90+3
Valencia: Diego Alves; Barragan, Mustafi, Otamendi, Gaya; Javi Fuego, Parejo (Filipe 84), Andre Gomes; Feghouli, Negredo (Alcacer 82), Rodrigo (De Paul 72)
Barcelona: Bravo; Dani Alves, Pique, Mathieu (Rakitic 69), Alba; Mascherano, Busquets, Xavi (Rafinha 80); Suarez (Pedro 80), Messi, Neymar
Referee: David Fernandez Borbalan
