The near-ultraviolet excited Zn3(VO4)2 phosphor film on a quartz substrate was fabricated by RF magnetron sputter deposition of the film at 150°C or room temperature and subsequent rapid thermal calcination at 600–900°C. The phosphor film exhibited a broad emission spectrum with a peak at 567nm and a FWHM of 186nm. The highest internal quantum efficiency of 45% was obtained after 800°C calcination of the 150°C-deposited film with a Zn/V molar ratio of 1.9. The 800°C calcination promoted a thermal coalescence and effectively reduced surface traps of Zn3(VO4)2 particles. Zn3(VO4)2 was thermally decomposed into Zn4V2O9 and Zn2V2O7 at 900°C, and the quantum efficiency decreased drastically as a consequence.