Hierarchical porous Co₃O₄ spheres were synthesized by a solvothermal method followed by high-temperature calcination. XRD, SEM, TEM and electrochemical tests were used to study the structure and performance of the hierarchical porous Co₃O₄ spheres. The results show that the Co₃O₄ synthesized at a calcination temperature of 700 °C (Co₃O₄-700) is micro-sized spheres (1-2 μm) consisting of plentiful nanoparticles (50-200 nm) and numerous pores (~100 nm). Due to its numerous porous morphology, the Co₃O₄-700 anode exhibits the highest cycling performance with excellent reversible discharge and charge specific capacities of 745 and 755 mA·h/g at the current density of 100 mA/g after 100 charge-discharge cycles, respectively.