Villarreal's unbeaten start continued with a 5-0 thrashing of Celta Vigo, whilst Athletic Bilbao's 3-2 win over Real Sociedad in the Basque derby means the top six are separated by just three points.
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Prandelli's Valencia off to winning start
Cesare Prandelli enjoyed the perfect start to life in charge of Valencia as Mario Suarez's double lifted Los Che out of the relegation zone with a 2-1 win at Sporting Gijon.
Cesare Prandelli (R) with Valencia's Singaporean President Lay Hoon Chan at the Mestalla stadium in Valencia on October 3, 2016
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Prandelli is Valencia's fourth coach in under a year, but got an instant response as Suarez finished off a fine team move to open the scoring after just seven minutes.
The former Italy boss signalled his priority is improving Valencia's defence, but they are still to keep a clean sheet this season as Carlos Castro headed home unmarked just before half-time.
However, former Atletico Madrid midfielder Suarez, who scored just five goals in nearly 200 games with Los Rojiblancos, was the unlikely Valencia hero once more when he coolly chested down a loose ball inside the area before smashing into the roof of the net 25 minutes from time.
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Villarreal moved level with Barcelona in fifth, two points off the top, with a surprising demolition of Celta at El Madrigal.
Celta had won their last four games in all competitions, including a 4-3 win over Barca last time out.
However, Roberto Soriano struck twice in the opening 12 minutes before Cedric Bakambu gave Villarreal a 3-0 half-time lead.
Celta's evening to forget was compounded by Daniel Wass' own goal and a red card for Sergi Gomez before Manu Trigueros rounded off the scoring in stoppage time.
Athletic moved to within three points of leaders Atletico Madrid with a 3-2 win over local rivals Sociedad in a pulsating Basque derby.
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Sociedad took the lead against the run of play when David Zurutuza volleyed home Xabi Prieto's corner on 17 minutes.
Athletic laid siege to the Sociedad goal, only to be denied by the outstanding form of Argentine international goalkeeper Geronimo Rulli before the break.
Iker Muniain finally levelled with a brilliant effort from outside the box that curled in off the far post to leave Rulli helpless six minutes into the second-half.
Sociedad then caused their own downfall as twice they were caught in possession deep inside their own half as Aritz Aduriz chipped home Athletic's second before teeing up Inaki Williams for the third.
Inigo Martinez's fine header from a narrow angle gave the visitors hope seven minutes from time, but Athletic held on for their first win over Sociedad since 2012.
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The top four were all victorious on Saturday as Atletico, Real Madrid and Barca thrashed Granada, Real Betis and Deportivo la Coruna respectively, whilst Sevilla sneaked past Leganes 3-2.
Earlier on Sunday, Roberto Rosales's stunning long-range effort five minutes from time salvaged a 1-1 draw for Malaga at Alaves.
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