Uniform zinc-cyanide hybrid coordination polymer microspheres were successfully synthesized by a coprecipitation method. Then hierarchical yolk-shell structured and carbon coated ZnO microspheres (YC-ZnO) composed of ZnO@C nanocrystals were prepared by consecutive post annealing processes of these microspheres in argon and air atmosphere. Such micro-nano porous structures have the advantages of large specific surface area, good charge transport kinetics, and large cavity to accommodate the volume change and maintain the mechanical integrity of the electrode material. When evaluated as anode materials of lithium ion batteries, these ZnO yolk-shell spheres exhibited excellent battery performance with a high rate capacity and ultra-stable cycling stability.