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Nanostructured NiPdCe particles be arc plasma method in Ar+H2 atmosphere were characterized by TEM, HRTEM and XRD. The results show that nanostructured NiPdCe particles possess the special Structure consisting of the thin-shell layer composed of a series of CeNi phases, Pd and CeO2 and the core composed of Ni and Pd. The thickness of the shell layer is 2~3 nm. The reactivity of nano-NiPdCe particles was measured in the gas-phase hydrogenation of toluene. The results show that nano-NiPdCe particles possess high reactivity above 325℃ and the product selectivity is 100%. The reactivity of nano-NiPdCe particles depends on the synergistic effects of CeNi phases, Ni and Pd as well as the hydrogen storage property.