Triple-shelled Co3O4 hollow spheres were successfully prepared using a facile solvothermal method and the following calcinations. Benefitting from the unique hollow structure, triple-shelled Co3O4 hollow spheres exhibited much higher specific reversible capacity (923.1 mA h g(-1)) than that of bare Co3O4 particles (206.9 mA h g(-1)) after 50 cycles, as well as superior rate capability. This is because of the porous shells, which can accommodate volume change during charging/discharging process and enable easy infiltration of electrolyte when used as anodes in lithium ion batteries.