Porous solid with multimodal pore size distribution provides plenty of advantages including large specific surface area and superior mass transportation to achieve high gas-sensing performances. In this study, α-Fe2O3 nanoparticles with bimodal porous structures were prepared successfully through a nanocasting pathway, adopting the bicontinuous 3D cubic symmetry mesoporous silica KIT-6 as the hard template. Its structure and morphology were characterized by X-ray diffraction, nitrogen adsorption-desorption, transmission electron microscopy, and so on. Furthermore, the gas sensor fabricated from this material exhibited excellent gas-sensing performance to several volatile organic compounds (acetone, ethyl acetate, isopropyl alcohol, n-butanol, ethanol, and methanol), such as ultrahigh sensitivity, rapid response speed (less than 10 s) and recovery time, good reproducibility, as well as stability. These would be associated with the desirable pore structure of the material, facilitating the molecules diffusion toward the entire sensing surface, and providing more active sensing sites for analytical gas.