Valencia were looking to build on their midweek result away to Manchester United in the Champions League with a stern opponent in the defending champions.
Ezequiel Garay send them into delirium with the opening strike in the opening minute following a corner kick.
Despite having the lead, the home side made an early change through injury as Denis Cheryshev entered for Goncalo Guedes on 11 minutes.
A minute later, Michy Batshuayi tested Marc Andre Ter Stegen with a shot from close range but the German stood his ground.
Barca got out of their shell and into their stride and Lionel Messi fired in a low shot but Neto came up with the goods.
The little magician produced the goods on 23 minutes after playing a one-two with Luis Suarez to blast home the equaliser.
It was all Barca after that, with Valencia having no time and space on the ball to conjur up any offensive moves.
The home side kept a good defensive shape despite the limited amount of chances to go into the break tied.
Valencia started the second half strongly after Cheryshev dribbled past a few defenders to shoot just over the bar.
Barca managed to put a move together on the edge of the area with Messi ending up with the shot away from an acute angle but Neto dealt with it well.
Daniel Parejo responded with a speculative volley from a distance, but the effort sailed wide of target.
As time ran by, Messi attempted to find the top corner with a well-driven strike but it headed well over the crossbar.
In the last few minutes, the Argentine attacker went close again after cutting inside to get a shot away from an acute angle but dragged the effort wide.
Following their Champions League master class in London, the poor run of form for the Catalans seems to be continuing with their fourth straight game without a win.