Luis Enrique's league leaders left the door ajar at the summit when they threw away a two-goal advantage to draw 2-2 at Sevilla, meaning Real Madrid now sit just two points behind in second.
Barca were back to their irresistible best in the UEFA Champions League on Wednesday as Luis Suarez netted a brilliant brace in an impressive 3-1 win at Paris Saint-Germain.
Their return to domestic action could be a testing one, with Valencia currently in possession of the fourth Champions League qualifying spot.
In the corresponding fixture last season, the visitors prevailed 3-2 thanks to goals from Dani Parejo, Pablo Piatti and Francisco Alcacer, with Alexis Sanchez and Lionel Messi on target for Barca, who had Jordi Alba sent off.
The Catalan giants ultimately missed out on the title by three points and will be keen for Valencia not to have such an influential say on proceedings this time around.
Defender Gerard Pique made his 300th appearance for Barca in Paris and has urged his team-mates to remain focused as a campaign where they could also claim the Copa del Rey moves towards its potentially glorious conclusion.
"We are very confident on the back of the results we have been earning this season," he said.
"We are aware of how difficult it is to have a chance in three different competitions. But we can't have a rest this Saturday against Valencia. It is so hard to keep going, but it is a challenge we can face.
"We have all learned a little bit. We had a lead against Sevilla and then they pulled one back and we let the game slip away."
Despite fifth-placed Sevilla's heroics last weekend, Valencia were able to edge three points clear of them in fourth thanks to a 3-0 win over Levante.
Alcacer opened the scoring before second-half strikes from Sofiane Feghouli and Alvaro Negredo moved Nuno Santo's team to within a point of champions Atletico Madrid in third.
Barca midfielder Andres Iniesta is a major doubt for the match having left the field on a stretcher in midweek. The club's official website confirmed that the Spain star had "suffered heavy bruising in the pelvic region".
Valencia duo Enzo Perez (thigh) and Piatti (hamstring) remain doubtful, while full-back Jose Luis Gaya has returned to full training following a hamstring problem.
