Preparation of conducting-polymer hollow nanoparticles with different diameters was accomplished by surfactant templating. An anionic surfactant, namely sodium dodecylbenzenesulfonate, formed vesicles to template with the pyrrole monomer. Subsequent chemical oxidative polymerization of the monomer yielded spherical polypyrrole (PPy) nanoparticles with hollow interiors. The diameter of the hollow nanoparticles was easily controlled by adjusting the concentration of the surfactant. Subsequently, the size-dependent electrochemical properties of the nanoparticles, including redox properties and charge/discharge behavior, were examined. By virtue of the structural advantages, the specific capacitance (max. 326 F g−1) of PPy hollow nanoparticles was approximately twice as large as that of solid PPy nanospheres. The hollow PPy nanostructure can easily be used as a conductive substrate for the preparation of metal/polymer nanohybrids through chemical and electrochemical deposition. Two different pseudocapacitive metal-oxide clusters were readily deposited on the inner and outer surfaces of the hollow nanoparticles, which resulted in an increase in the specific capacitance to 390 F g−1. In addition, the hollow nanoparticles acted as a nanocage to prevent metal ion leaching during charge/discharge, thus allowing an excellent capacitance retention of ca. 86%, even following 10,000 cycles.