A facile and low-cost preparation of Pd nanoparticles on the surface of hollow polypyrrole (ppy) nanospheres was introduced in this paper through solvothermal reaction. Herein, uniform polystyrene (PS) microspheres as sacrificial templates were rapidly prepared through a emulsion polymerization method, and then the hollow ppy nanospheres were obtained through chemical oxidative polymerization of pyrrole in the presence of PS microspheres. According to X-ray diffraction (XRD) and transmission electron microscopy (TEM) measurements, the novel Pd nanoparticles are well-dispersed on the surface of hollow ppy nanospheres with a relatively narrow particle size distribution. The diameters of hollow ppy nanospheres range from 240 to 280 nm, and the average shell thickness is about 15 nm. Electrochemical analysis results indicate that the as-prepared Pd nanoparticles on the surface of hollow ppy nanospheres (Pd/H-ppy) exhibit good electrocatalytic activity and stability for ethanol electro-oxidation. (C) 2015 Elsevier Ltd. All rights reserved.