A series of silver catalysts supported on lanthanum based perovskites LaBO3 (B = Co, Mn, Ni, Fe) were synthesized and evaluated in the catalytic oxidation of ethyl acetate. XRD, BET, TEM/HRTEM, HAADF-STEM, XPS and H-2-TPR were conducted, and the results indicate that redox activity of the catalysts is of great importance to the oxidation reaction. Activity tests demonstrated that Ag/LaCoO3 was more active than the other samples in ethyl acetate oxidation. Moreover, the CO2 selectivity, COx yields and byproduct distributions for all catalysts were studied, and Ag/LaCoO3 showed the best catalytic performance. Besides, Ag/LaCoO3 also showed excellent catalytic activity for other OVOCs.