The synthesis of ZnO with tailorable shapes and point defects is important for its potential applications. Here, a facile approach is demonstrated to prepare ZnO nanocages with controllable porous shell structures though sintering a Zn-based cyanide-bridged coordination polymer under different temperatures. The transformation of ZnCP microspheres into ZnO nano cages is based on two types of nanoscale Kirkendall effect, which are related to low temperature solid-solid interfacial oxidation and high temperature solid-gas interfacial reaction, respectively. At low temperature (around 300 degrees C) and before the ZnCP decomposition, the novel "hierarchical ZnO bigger nanocages embedded with smaller nanocages with 10 nm nanocrystals" can be generated. By contrast, when coming to the total decomposition of ZnCP at 800 degrees C, ZnO nanocages with significantly increased sizes and large cavities are generated, and large amounts of oxygen vacancies (V-O) are created at the same time, leading to the dramatic increased luminescence intensities of the UV peak due to V-O at 540 nm. Thus, the luminescence intensities versus defect concentration in the prepared ZnO nanocages can also be controlled by tuning the sintering temperatures.