In this paper, ZnSe films were prepared on quartz substrates by selenizing as-sputtered zinc films at different temperatures for 6 h. The crystal structure, morphology, microscopic defects and optical properties of the ZnSe films were characterized by XRD, SEM, Raman spectroscopy, UV–visible spectrophotometer and slow positron beam Doppler broadening spectroscopy, respectively. The results showed that ZnSe thin films had the best structural and optical properties when the selenization temperature was 700 °C . All ZnSe thin films have a hexagonal wurtzite structure. The results of XRD、SEM and Raman spectra all showed that the crystallization and molar ratio of the films were significantly optimized with the increase of temperature. The transmission spectra of the films showed an obvious absorption edge of ZnSe and increased transmittance with the increase of temperature. The variation of defect concentration and types in the ZnSe thin films were released visually by slow positron beam Doppler broadening energy spectra.