The chemical composition, crystalline structure, surface morphology and photoluminescence spectra of Na-doped ZnO thin films with different heat treatment process were investigated by X-ray photoelectron spectroscopy, X-ray diffraction, atomic force microscopy and a fluorescence spectrometer. The results show that preferred orientation, residual stress, average crystal size and surface morphology of the thin films are strongly determined by the preheating temperature. The effects of preheating temperature on microstructure and surface morphology have been discussed in detail. The photoluminescence spectra show that there are strong violet & UV emission, blue emission and green emission bands. The violet & UV emission is ascribed to the electron transition from the localized level below the conduction band to the valence band. The blue emission is attributed to the electron transition from the shallow donor level of oxygen vacancies to the valence band, and the electron transition from the shallow donor level of interstitial zinc to the valence band. The green emission is assigned to the electron transition from the level of ionized oxygen vacancies to the valence band.