The most effective catalyst in H2-rich atmosphere for CO-PROX reaction is the CuO-CeO2 catalysts. In this experiment, a series of CuO-CeO2@SiO2 catalyst with different ratio of CuO and CeO2 had been synthesized by two-step hydro-thermal method and impregnation method. The catalysts were characterized by X-ray diffraction (XRD), surface area analysis (BET), scanning electron microscope (SEM), transmission electron microscopy (TEM) and catalytic-performance test for CO-PROX reaction in H2-rich atmosphere. The results showed that CuO-CeO2@SiO2 catalysts had large specific surface area. Whether the ratio of CuO and CeO2 is higher or lower, the performance of the catalysts will been influenced, with the CeO2@SiO2 having been covered by CuO, the performance of which is not ideal with the higher ratio, with the same result of the lower ratio for the small amount of the CuO. The results showed that CuO-CeO2@SiO2 catalysts had better performance when the ratio of CuO and CeO2 was 3:7.