Designing sensing materials with integrating unique spatial structures, functional units, and surface activity is vital to achieve high-performance gas sensor toward triethylamine (TEA) detection. Herein, a simple spontaneous dissolution is used with subsequent thermal decomposition strategy to fabricate mesoporousized ZnO holey cubes. The squaric acid is crucial to coordinate Zn2+ to form a cubic shape (ZnO-0) and then tailor the inner part to open a holey cube with simultaneously mesoporousizing the left cubic body (ZnO-72). To enhance the sensing performance, the mesoporous ZnO holey cubes have been functionalized with catalytic Pt nanoparticles, which deliver superior performances including high response, low detection limit, and fast response and recovery time. Notably, the response of Pt/ZnO-72 towards 200ppm TEA is up to 535, which is much higher than those of 43 and 224 for pristine ZnO-0 and ZnO-72. A synergistic mechanism combining the intrinsic merits of ZnO, its unique mesoporous holey cubic structure, the oxygen vacancies, and the catalytic sensitization effect of Pt has been proposed for the significant enhancement in TEA sensing. Ourwork provides an effective facile approach to fabricate an advanced micro-nano architecture with manipulating its spatial structure, functional units, and active mesoporous surface for promising TEA gas sensors.