Diffusion Reflectance Spectroscopy (DRS) was employed to study the surface phase structure of ZrO2-based catalysts. The effect of calcining temperature, and the addition of Al2O3 and platinum on the surface and bulk phase structures of zirconia was studied by DRS combined with XRD, DTA and XPS. The same trend was observed that heating to higher temperatures results in the conversion to monoclinic zirconia in undoped samples, while incorporation of an appropriate amount of Al2O3 would stabilize the tetragonal phase zirconia. And the reduction processing of Pt/ZrO2 affects crystallization and phase transitions, resulting in certain fraction of tetragonal ZrO2 transferred to monoclinic ZrO2. The DRS shows an appreciable difference in the corresponding XRD spectra that more monoclinic zirconia formed on the surface of catalyst during the reduction processing of Pt/ZrO2, compared to the bulk of catalyst.