In this work, we report a novel strategy for the controlled synthesis of nanorod assembled multi-shelled cobalt oxide (Co3O4) hollow microspheres (HSs). The Co2CO3(OH)(2) NRs are first vertically grown on the carbon microspheres (CS) to form the core-shelled composites by a low-temperature solution route. The multi-shelled hollow interiors within the Co3O4 microspheres are unconventionally obtained by annealing the as-prepared core-shell structured CS@Co2CO3(OH)(2) composite in air. When evaluated for supercapacitive performance, the multi-shelled Co3O4 hollow microspheres exhibit high capacitance of 394.4 and 360 F g(-1) at the current densities of 2 A g(-1) and 10 A g(-1), respectively. The superior electrochemical performance can be attributed to the multi-shelled hollow structures, which facilitate the electrolyte penetration and provide more active sites for the electrochemical reactions. (C) 2014 Elsevier B.V. All rights reserved.