The visitors who the Estadio Jose Zorrilla hadn't won in any of their last eight LaLiga Santander fixtures and have been dragged towards the foot of the table.
Los Che's captain did eventually find the net, though, beating Masip for power with a strike from distance with 15 minutes remaining.
Manu Vallejo thought he'd added a second goal for Gracia's side, only to be denied when VAR spotted an offside in the build-up.
Valencia held on for a vital three points, though, moving as many points clear of the relegation zone and soaring as high as 13th in the table. Valladolid drop to 16th.