The multishelled (Co2/3Mn1/3)(Co5/6Mn1/6)2O4 hollow microspheres with controllable shell numbers up to septuple shells are synthesized using developed sequential templating method. Exhilaratingly, the septuple-shelled complex metal oxide hollow microsphere is synthesized for the first time by doping Mn into Co3O4, leading to the change of crystalline rate of precursor. Used as electrode materials for alkaline rechargeable battery, it shows a remarkable reversible capacity (236.39 mAh g−1 at a current density of 1 A g−1 by three-electrode system and 106.85 mAh g−1 at 0.5 A g−1 in alkaline battery) and excellent cycling performance due to its unique structure.