Ni-V-O/SiO2 catalysts were prepared by impregnation methods and characterized by XRD, UV-Vis and pyridine adsorbed FTIR. The effects of treatment temperature and Ni-V ratio of the catalysts on photocatalytic catalysis of carbonylation for methonal with carbondioxide were investigated under UV irradiation. The results indicated that the selectivity of methyl formate (MF) and dimethyl carbonate (DMC) could be up to 77.6% when the catalyst with 6:4 of Ni-V ratio was treated at 60 °C. Pyridine-FTIR analyses revealed that the catalyst surface contained Lewis acid sites and the acid content obtained by calculation was 1.85 mmol/g. The surface L acid strength was the major factor to influence the selectivity of carbonylation products.