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Palladium hollow spheres were synthesized at room temperature using cobalt nanoparticles (NPs) as sacrificing templates. Cobalt NPs can be prepared simply by solvothermal method. The hollow nature of sample Pd were observed from the TEM image and the SAED pattern indicates the polycrystalline nature of the sample. It was found that Pd hollow spheres showed high catalytic activity towards the electrooxidation of alcohols, especially ethanol with the current density up to 2047 mA•mg-1. The formation mechanism and the structure-property relationship of Pd hollow spheres were discussed based on the experimental results.