The high sensing performance of chemical sensing sensors depends greatly on rational design of nanostructure and smart heterogenization of tailorable nanomaterials. Hybrid materials (HMs) as active sensing layers, are generally used for sensing devices. Here, the heteroassembly of n-type α-Fe2O3nanoparticles on a p-type LaFeO3 matrix into a pore-rich hollow nanostructure is reported. The fabrication process uses a hydrothermal and co-precipitation synthesis method and begins from carbon nanospheres as sacrificial templates. The hetero-interfacial area and surface structure can be successfully tailored by changing the composition ratio of α-Fe2O3 to LaFeO3. Consequently, as sensing materials in gas sensors, the α-Fe2O3/LaFeO3 hetero-materials have a fast response/recovery time of 1 s/5 s after 5 cycles and are able to retain 92.4% of this sensitivity after 15 days, i.e., 10.1, to 100 ppm ethanol gas, which is closely related with the strong hetero-interfacial contact and unique hollow structures. This work offers a new insight into the rational design of chemical sensing devices from the synergetic effect of p-type ternary transition metal oxides as well as n-type nanostructures.