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A series of supported catalysts Co3O4/SiO2 were prepared by deposition precipitation method. ICP-AES, XRD and TEM data revealed that the Co3O4 active site was highly dispersed on the surface of SiO2. The catalysts were evaluated for selective epoxidation of styrene with molecular oxygen. The results showed that the catalysts were of good catalytic activity for styrene epoxidation and many factors had an evident effect on the catalytic epoxidation activity. The best catalyst was 3% Co3O4/SiO2 on which 96.3% conversion of styrene and 52.7% selectivity of styrene oxide were obtained under the flow rate of O2 20mL/min, 100℃, 10h with solvent.