Rodrigo, Spain International signs a four-year record deal contract with English premier league club, Leeds United.
The deal reportedly cost the Premier League newcomers around £30 million ($40 million).
The 29-year-old said he was excited to join the club and was looking forward to working with Marcelo Bielsa, whom he described as one of the best coaches in football.
“It’s a new step in my career and I want to help the team to achieve the goals of the season,” he told the club’s Twitter account.
“Leeds have been working for two weeks on this deal with Valencia — we knew Valencia have some problems now as we didn’t achieve the Champions League.
“Since the first time Victor (Orta, director of football) talked to me I knew I wanted this new challenge with Leeds.”
Rodrigo, who can operate as a winger or striker, spent time at Celta Vigo and Real Madrid as a young player before moving to Benfica.
He joined Valencia in 2014, initially on loan, scoring 59 goals in 220 appearances.
He scored 10 goals for club and country in 38 games last season, including the winner in Valencia’s 1-0 Champions League win at Chelsea in September.