Valencia's last win came courtesy of goals from Miguel Angel Angulo and David Silva, while Ronaldinho grabbed a late consolation for the visitors, who finished second to Real Madrid by virture of head-to-head record that season.
Both teams are under new managers this term, and this clash represents a chance to pick up a first high-profile league scalp of the 2013-14 season.
Gerardo Martino has kicked off his Barca tenure with two league wins - 7-0 against Levante and 1-0 against Malaga - and also oversaw victory in the two-legged Supercopa de Espana final against Atletico Madrid.
Miroslav Djukic, meanwhile, began his spell in charge with a 1-0 win over Malaga at home, though that was followed up with a 3-1 away defeat to Barca's city rivals Espanyol.
Barcelona's exploits have seen them take an early lead in La Liga as they look for their fifth title success in six seasons.
Valencia's aims this term are likely to involve sealing a return to the UEFA Champions League after they were denied qualification by Real Sociedad on the last day of 2012-13.
Barca academy graduate Oriol Romeu has yet to feature for the Mestalla club since sealing a season-long loan move from Chelsea, but would face his former club for the first time since leaving should he feature.
Valencia and Barcelona shared a 1-1 draw in this fixture last year, with Ever Banega opening the scoring before Lionel Messi equalised from the spot.
The latter player in fact missed a penalty in Wednesday's 0-0 draw with Atletico, but has still scored two goals in his three outings so far this term.
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