The 28-year-old’s contract expired at the end of last month and no new deal was signed, allowing the academy graduate to leave Camp Nou and begin talks with other clubs.
Masip has now agreed a three-year deal with Valladolid, who finished seventh in the second tier last season.
“Jordi Masip Lopez has become the eighth Real Valladolid signing for the 2017-18 season,” the club confirmed in a statement.
“The Catalan, third goalkeeper of the Barcelona team over the last three seasons, signs until June 30, 2020.”
Masip made his competitive debut in an 8-1 Copa del Rey thrashing of Huesca in December 2014 but he only made three further appearances for Barca.