Nano-Ce / CuO desulfurizers modified by iron, cobalt and zinc were prepared by direct deposition precipitation, and the performance of the nanoparticles for H2S desulfurization at ambient temperature was evaluated by the break-through tests. X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and other characterization means were adopted to explore relationship between structural changes and desulfurization performance. The results indicate that nano-Ce / CuO desulfurizer modified by cobalt has the best desulfurization activity, and decreased significantly in particle size, and increased in the molar ratio of Cu3 /Cu2 , which was in favor of the oxygen vacancies increased in the surface; When the addition amount of Co in Ce / Cu desulfurizer is 4.9%, it exhibits best desulfurization activity with a H2S breakthrough time of 525 min, this extended nearly more 300 min than Ce / CuO desulfurizer.