Novel hierarchical ZnO hollow cubes are constructed using the interpenetrated 0D nanoparticles through directly decomposing the Zn-based metal–organic frameworks (Zn-MOF, ZIF-8). After decomposition at 450 °C for 1 h, the as-prepared ZnO well maintains the original ZIF-8 shape with relatively high surface area (45 m² g⁻¹), thereby realizing fast surface reaction kinetics of benzene molecules. In contrast to singular 0D ZnO nanoscale counterparts, the unique ZnO nanostructure assembly renders the well exposed surfaces and defect states, enhancing significantly chemical sensitivity towards gaseous benzene. The present work provides a facile and versatile approach for designing the high-performance chemical sensing materials.