Cancelo joined Valencia on August 20, 2014 on a one year loan, with an option to buy for €15 million. He made his La Liga debut on September 25 2014, in a 3-0 win against Córdoba. He was awarded the man of the match on April 12, 2015, after a 3-0 win against Levante. He only made 13 appearances in the 2014-15 season, as he was mainly the backup of Antonio Barragán. On May 25, Cancelo agreed a permanant contract with Valencia until June 30, 2021. The transfer fee was €15 million.