Novel porous CuO/Cu2O@CeO2 anode has been successfully synthesized from a Cu-based metal-organic framework (Cu-MOF) via a simple two-step pyrolysis method. The CeO2 protective layer greatly improves the electronic conductivity, can buffer the volume change and can provide pathways for electron transport and Li+ diffusion. The results demonstrate that the electrochemical performance of CuO/Cu2O anode can be significantly improved by the design. The CuO/Cu2O@CeO2 electrode delivers a large specific capacity of 473 mAh g(-1) at 0.3 A g(-1), and exhibits excellent rate capacity with 250 mAh g(-1) at 2 A g(-1) and good cyclic performance with a capacity of 592.3 mAh g(-1) after 100 cycles at 0.2 A g(-1).