The design and synthesis of hierarchical hollow microcubes are demonstrated as a sensing material for H₂S gas detection. The hierarchical hollow microcubes are functionalized by Pt catalysts, assembled from the hierarchical hollow Co₃O₄microcubes and coated with nickel oxide nanoplates. The template-engaged synthesis of Co-PBA@Ni(OH)₂microcubes is an etching-deposition-growth hydrothermal process. The gas sensing performances of the sensors based on pure Co₃O₄microcubes, pure NiO, Co₃O₄@NiO microcubes, Co₃O₄@Pt microcubes, NiO@Pt and Co₃O₄@NiO@Pt microcubes are systematically investigated. Benefitting from the synergistic effects of the diverse compositions, the advantages of the hierarchical hollow microstructure, a higher surface area of 65.5 m²/g compared with pure Co-PBA microcubes (4.0 m²/g), the p-pheterojunction between Co₃O₄/NiO, the Schottky barrier amongst NiO/Pt as well as the efficient catalytic activity of Pt, the gas sensors based on Co₃O₄@NiO-2.0@Pt3.0 microcubes with Pt at 3.0 wt% manifest boosted selectivity, together with enhanced sensing responses (∼250.0 towards 100 ppm H₂S) at the optimal working temperature of 200 °C. The response is nearly 78-fold greater than that of the devices based on pure Co₃O₄(3.2). Additionally, Pt can dramatically enhance the selectivity to H₂S sensors. The enhanced sensing performance of the sensors based on Co₃O₄@NiO-2.0@Pt3.0 microcubes can also be attributed to the chemical and electronic sensitization of Pt doping as well as the high resistance.