In this work, we report a Pd-around-CeO_2−x hybrid nanostructure catalyst for direct ethanol fuel cells, which is synthesized via a facile three-phase-transfer approach. The obtained nanostructure catalyst is characterized by X-ray diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy. In this nanostructure, Pd nanoparticles (NPs) are closely attached onto the surface of the CeO_2−x NPs, leading to an intense interfacial interaction between Pd and CeO_2−x. The electrocatalytic properties of the Pd-around-CeO_2−x hybrid nanostructure catalyst for ethanol electrooxidation is investigated by cyclic voltammetry and chronoamperometry. This Pd-around-CeO_2−x hybrid nanostructure catalyst shows a superior catalytic performance for ethanol electrooxidation, which can be attributed to a novel dual promoting mechanism.