Hollow polyaniline microspheres (HMsPANI) for supercapacitors were prepared successfully with sulfonated polystyrene microspheres as the template. The prepared electrode materials of HMsPANI consisted of nanoparticles and, thus, had a hierarchical structure. The electrochemical behaviors of the materials were investigated with cyclic voltammetry and galvanostatic chargedischarge tests. A maximum specific capacitance of 421 F/g was achieved in a 1M H2SO4 solution, with the potential ranging from -0.2 to 0.8 V (vs a saturated calomel electrode), in a three-electrode glass cell at room temperature for the HMsPANI electrode. This suggested its potential application in electrochemical capacitors. (c) 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 127: 1544-1549, 2013