The study was performed on hafnia thin films deposited with electron beam evaporation deposition before and after annealing. The transmittance,X-ray diffraction (XRD) and photoluminescence (PL) excitation spectrum of the samples were tested to analysis the property and structure of the film. Intensity of the photoluminescence increases after the annealing process. It is found that the Stokes shift is existed between excitation spectrum and emission spectrum. XRD shows that after annealing,the orientation and the crystalline are markedly improved. The annealing process has no effect upon the laser-induced damage threshold (LIDT).