The Yellow Submarine conceded two late goals to lose against Sevilla on Sunday, but Marcelino's team have still made a strong start to the season, with 14 points from nine games leaving them eighth in the table.
Valencia, meanwhile, have lost just once this term, with a total of 20 points leaving them in fourth, just two points from leaders Barcelona.
"This is a great game and our opponents will be coming here with a lot of hope, so we must match them or do even better. It's also one where special conditions apply and we are very fortunate to be able to play in it," he told reporters.
"Valencia are very different from last year in that they have a young team with exceptional quality and they are one of our direct rivals for a place near the top. There's a lot of rivalry, so that makes it particularly unique, and they'll be coming to win after we beat them last year, but we also need to win."
Villarreal have lost two of their four home league games this season.