Lionel Messi’s 500th career goal could not prevent stumbling leaders Barcelona suffering a third successive La Liga defeat for the first time since 2003.
Ivan Rakitic deflected Guilherme Siqueira’s cross-shot into his own net to give Valencia a shock lead.
Santi Mina then finished a terrific move by slotting in a second goal in first-half stoppage time.
Messi ended a club goal drought of 515 minutes, but Barcelona now only lead Atletico Madrid on goal difference.
Luis Enrique’s side began April with a nine-point lead over second-placed Atletico, but their season has crumbled since then, with defeat against Real Madrid in El Clasico marking the start of a dreadful run.
It was Atletico who ended Barcelona’s chances of retaining the Champions League in midweek, and who drew level at the top of La Liga with a comfortable 3-0 victory over Granada earlier on Sunday.
Barca, playing the 53rd match of a draining season that included a trip to Japan in December to win the Club World Cup, looked weary and short of ideas as they attempted to fight back from a 2-0 half-time deficit.
They could lose top spot if they fail to win at Deportivo La Coruna on Wednesday, with Atletico visiting Athletic Bilbao on the same night, and Real Madrid – just a point behind in third place – also in action, at home to Villarreal. BBC Sport
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