Barca drop first points of season
Barca had won six on the trot before their trip to the Mestalla but struggled to get any rhythm going in the face of intense pressure from the hosts.
Keeper Victor Valdes made some decisive interventions and all Valencia lacked was the cool finishing of top scorer David Villa, who failed to recover from injury in time for the game.
"Valencia have very good players and a very good coach and caused us a lot of problems," Barca coach Pep Guardiola told reporters. "We have to be happy with the point."
Barca remain top with 19 points from seven matches, one point ahead of Real Madrid who returned to winning ways with a 4-2 home victory over Real Valladolid.
Deportivo Coruna are fourth on 15 points, the same as third-placed Sevilla, after Juan Rodriguez's spectacular strike gave Depor a 1-0 home win over the in-form Andalucians.
The midfielder crashed in a 30-metre drive in the 38th minute and Deportivo's well-organised defence kept the visitors at bay to end Sevilla's run of seven consecutive wins in all competitions.
Barca had Zlatan Ibrahimovic on the bench and Thierry Henry out injured in Valencia and it was Valdes and his defence who were busiest as the home side broke forward with pace at every opportunity.
Valdes denied Pablo Hernandez after two minutes and pulled off another one-on-one save from David Silva after a quickly taken free kick in the second period.
Although Valencia tired as the second half progressed Barca made little headway in an increasingly bad-tempered affair.
Earlier, Gonzalo Higuain came off the bench to settle Real Madrid's jitters with a superb lob that completed their victory over Valladolid.
Manuel Pellegrini's side, who were without injured forward Cristiano Ronaldo, had suffered their first defeat of the campaign in Sevilla last time out.
Raul scored twice in quick succession against Valladolid and Marcelo added a third before the break after Nauzet Aleman had netted a superb free kick for the visitors.
Marquitos put Valladolid back in the game again early in the second half and they grew in confidence until Argentine substitute Higuain lifted the ball over Jacobo in a one-on-one 11 minutes from time.
"Scoring four goals is good for the team and the fans," said Pellegrini. "We made a couple of errors that allowed Valladolid into the game but it would be wrong to say our defence was weak.
"In general we played a good first half but in the second we were inconsistent."