A facile two-step annealing process is applied to synthesize nanocage Co3O4, using cobalt-based metal-organic framework as precursor and template. The as-obtained nanocages are composed of numerous Co3O4 nanoparticles. N2 adsorption–desorption isotherms show that the as-obtained Co3O4 has a porous structure with a favorable surface area of 110.6 m2 g−1. Electrochemical tests show that nanocage Co3O4 is a potential candidate as anode for lithium-ion batteries. A reversible specific capacity of 810 mAh g−1 was obtained after 100 cycles at a high specific current of 500 mA g−1. The material also displays good rate capability, with a reversible capacity of 1069, 1063, 850, and 720 mAh g−1 at specific current of 100, 200, 800, and 1000 mA g−1, respectively. The good electrochemical performance of nanocage Co3O4 can be attributed to its unique hierarchical hollow structure, which is maintained during electrochemical cycling.