[en] Highlights: • Hierarchical yolk shell structures assembled from [email protected] nanocrystals were successfully prepared from zinc-cyanide hybrid coordination polymers. • The micro-nano secondary structure can both achieve high packing density and facilitate the Li⁺ ion diffusion. • The yolk-shell structure exhibit ultra-stable cycle life because it can further buffer the strain during repeated cycling to maintain the structural integrity. 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 [email protected] 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.