GdVO4 (GVO) thin films were successfully deposited on n-GaN/Al2O3 substrates used as a bottom electrode at 600 °C by radio frequency magnetron sputtering. The GVO films annealed at temperatures up to 800 °C exhibited epitaxial growth but the films annealed above 900 °C showed polycrystalline properties. In the photoluminescence (PL) spectrum, broadband emission was observed at 450 nm for all the films. The auger electron spectroscopy (AES) line-shape of the annealed films was similar to that of the as-deposited film but the Gd/V and Gd/O ratios increased linearly with increasing annealing temperature. The dielectric constant and dielectric loss of the GdVO4 films decreased with increasing annealing temperature with values of 12–26 and 0.04–0.05 at 1 MHz, respectively.