With diethylamine as a solvent, ZnSe films were formed on the Si substrate directly from zinc and selenium through the modified solvothermal method. The effects of holding temperature, deposition time and substrate surface treatment on the quality and morphologies of the ZnSe films were investigated. The growth mechanism of ZnSe films was proved to be a layer-nucleation growth process, which was tied in with the Stranski-Krastanov (SK) model. ZnSe films were identified by the X-ray diffraction pattern (XRD), the scanning electron microscope (SEM), the X-ray photoelectron spectroscope (XPS) and the photoluminescence (PL) techniques. The results indicate that the modified solvothermal method with diethylamine as a solvent is suitable to prepare high quality ZnSe films.