Using SiO2, activated carbon (AC) and Al2O3 as supports, the supported photocatalysts Ni-V-O/SiO2, Ni-V-O/AC and Ni-V-O/Al2O3 were prepared by impregnation method, and their spectralsignatures were investigated.The carbonylation of methanol with CO2 under UV irradiation was used as a probe reaction to compare the photocatalytic performance of the prepared catalysts.Integrated with the testing results of carbonylation, the effects of different supports on selectivity for the carbonylation products of methyl formate (MF) and dimethyl carbonate (DMC) were discussed by pyridine-IR and UV-Vis techniques.XRD results showed that the particles of nickel and vanadium supported on SiO2 had the highest degree of dispersion.Results of pyridine-IR indicated that all catalysts retained Lewis acid sites.The acid strength was different from catalyst samples with different supports but with the same active components.The acid strengths could be arranged as follows: Ni-V-O/SiO2>Ni-V-O/Al2O3>Ni-V-O/AC.Different acid strengths exhibited different influence on the selectivity of products MF and DMC of carbonylation.The surface acid strengths of catalysts were the major factor influencing the selectivity of carbonylation products.