Hollow porous ZnO/C nanocages were synthesized by pyrolysis of hollow MOF-5. The hollow porous ZnO/C nanocages were potentially useful for rechargeable LIBs. The ZnO/C released an initial discharge capacity of 1928 mA h g−1 at 100 mA g−1. The ZnO/C remained a high reversible capacity of 750 mA h g−1 after 100 cycles. The ZnO/C also exhibited an exceptional rate capability of 351 mA h g−1 at 2 A g−1.