Meso-macroporous monolithic CuO-CeO2/gamma-Al2O3 catalysts were prepared and tested for preferential oxidation of carbon monoxide in hydrogen-rich gases. The catalysts were characterized with photographs, SEM, N-2 adsorption-desorption, XRD, HRTEM, and TPR techniques. CuO-CeO2 catalysts were evenly coated onto the walls of gamma-Al2O3 monolith macropores with ceria and copper oxide highly dispersed. The prepared meso-macroporous monolithic CuO-CeO2/gamma-Al2O3 catalysts can remove CO from H-2-rich gases to ppm level at high space velocity, indicating that they are a kind of promising structured catalyst.