The hierarchical hollow manganese oxide nanospheres with both a large surface area and a layered structure have been successfully prepared by a templating-assisted hydrothermal process at 150 degrees C for 48 h. SiO2 template spheres are dispersed in KMnO4 Solution, and then followed by hydrothermal treatment to forming silica/manganese oxide nanospheres with a core-shell structure. The core-shell nanospheres are etched in a NaOH solution (20 wt.%), so that the SiO2 core is removed, and the hierarchical hollow manganese oxide nanospheres are obtained. The as-synthesized hierarchical hollow manganese oxide nanospheres present a birnessite-type manganese oxide phase with a chemical composition of Na0.38MnO2.14 center dot 13H(2)O, and a specific surface area of 253 m(2) g(-1). The prepared materials exhibit an ideal capacitive behavior and good cycling stability in a neutral electrolyte system and the initial capacitance value is 299 Fg(-1). Some preparation conditions including the hydrothermal temperature, dwell time and concentration of template have been also investigated. (C) 2009 Elsevier B.V. All rights reserved.