ZnO thin films were deposited on the substrates of (100) γ-LiAlO2 at 400, 550 and 700℃ using pulsed laser deposition (PLD) with the fixed oxygen pressure of 20 Pa, respectively. When the substrate temperature is 400℃, the grain size of the film is less than 1 μm observed by Leitz microscope and measured by X-ray diffraction (XRD). As the substrate temperature increases to 550℃, highly-preferred c-orientation and high-quality ZnO film can be attained.While the substrate temperature rises to 700℃, more defects appears on the surface of film and the ZnO films become polycrystalline again possibly because more Li of the substrate diffused into the ZnO film at high substrate temperature. The photoluminescence (PL) spectra of ZnO films at room temperature show the blue emission peaks centered at 430 nm. We suggest that the blue emission corresponds to the electron transition from the level of interstitial Zn to the valence band. Meanwhile, the films grown on γ-LiAlO2 (LAO) exhibit green emission centered at 540 nm, which seemed to be ascribed to excess zinc and/or oxygen vacancy in the ZnO films caused by diffusion of Li from the substrates into the films during the deposition.