In this work, we propose a facile and efficient strategy for mitigating capacity fading of ZnO by co-hybridization of cobalt (Co) and N-doped carbon (C–N). The ZnO-based hybrid (ZnO/Co/C–N) is prepared by calcining metal-organic frameworks (MOFs) under a vacuum condition. In view of the unique microstructure of MOFs used in our case, the resultant hybrid displays a three dimensional (3D) spherical morphology with abundant pore structure. The electrochemical tests indicate that the ZnO/Co/C–N nanospheres exhibit excellent cycling stability, high specific capacity, and good rate capability. This work proposes a facile strategy for the synthesis of nanomaterials with unique microstructure, desired composition and high surface area, endowing an excellent lithium storage performance. The current route is convenient and cost-effective, and therefore it is highly promising for scaled-up production. Moreover, the method we adopted may be extended to synthesize other porous nanomaterials with desired composition.