The design and synthesis of nanostructured ZnO with high chemical sensing properties, especially towards ppb or sub-ppm level VOC gases is still highly desired and challengeable. Herein, the hierarchical hollow ZnO nanocages were synthesized by a facile strategy through the simple and direct pyrolysis of Zn-based metal-organic framework. The as-synthesized hollow ZnO products present the typical hierarchical structures with hollow interiors enveloped by interpenetrated ZnO nanoparticles as porous shell, providing structurally combined meso-/macro-porous channels for facilitating the diffusion and surface reaction of gas molecules. The gas-sensing experiments demonstrate that, in contrast with singular ZnO nanoparticles, the ZnO nanocages show significantly enhanced chemical sensing sensitivity and selectivity towards low-concentration volatile organic compounds, typically, acetone and benzene. Furthermore, the ZnO hollow nanocages perform sub-ppm level sensitivity with 2.3 ppm-1 towards 0.1 ppm benzene, and ppb level sensitivity with 15.3 ppm-1 towards 50 ppb acetone, respectively. The enhanced sensing performance of the MOF-derived ZnO nanocages is ascribed to the unique hierarchical structure with high specific surface area and abundant exposed active sites with surface-adsorbed oxygen.