The home side went behind after 37 minutes when Pablo Hernandez scored for the visitors.
But second half goals from Andres Iniesta and Carles Puyol ensured that Barca secured all three points -- something they have struggled to do at home so far this season, dropping five points in their first three home games.
David Villa, who was facing his old club for the first time since his €40 million ($55 million) summer transfer, had several chances to score but was denied by some excellent saves from Valencia's keeper Cesar Sanchez.
The win puts Barcelona level on 16 points with Valencia at the top of La Liga.
Earlier Atletico Madrid secured a 2-0 win over Getafe at the Vicente Calderon stadium. The victory moves them to within three points of the top spot.
An own goal from Getafe keeper Jordi Codina in the first half saw Atletico take the lead. A Diego Costa strike after 72 minutes sealed the points helping the reigning Europa League champions move up to fifth place.
Meanwhile in Italy, two goals from Brazilian striker Alexandre Pato helped AC Milan to a 3-1 victory over Chievo at the San Siro on Saturday.
Pato's brace made it four goals in as many games for the 21-year-old, while Robinho scored his first goal for the club in the 90th minute to make sure of the victory.
The win puts Milan top of Serie A for the first time this season, ahead of Lazio who play Sunday.
In Saturday's other game, Roma beat Genoa 2-1
thanks to goals from Marco Borriello and Matteo Brighi. Genoa only goal came
courtesy of Gergely Rudolf in the 78th minute
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