The inverse CeO 2 /CuO catalysts were prepared by different precipitants, and characterized via XRD, ICP, SEM, H 2 -TPR, Raman, TEM and N 2 adsorption-desorption techniques. The study showed that the inverse CeO 2 /CuO configurations were formed and copper is mainly present in the form of bulk CuO in the as-synthesized catalysts.It was found that the length of the contact interface between CeO 2 and CuO was closely associated with the crystal size of CeO 2 and CuO. The CeO 2 /CuO catalysts using urea, NaOH and TMAH (tetramethylammonium hydroxide) as precipitants presented a better catalytic performance for CO oxidation below 185 °C in the hydrogen-rich streams due to some amount of copper-ceria interfacial sites in the catalysts.