The SnO2:Sb films have been prepared on sapphire (0001) substrates by radio frequency magnetron sputtering method. The structural and photoluminescence (PL) properties of the films were investigated. The prepared samples are polycrystalline films with rutile structure of pure SnO2. The photoluminescence of the samples was measured at room temperature. An ultraviolet luminescence peak near 334 nm was observed for the first time and the corresponding PL mechanism was investigated.