Hierarchical alpha-Fe2O₃/NiO composites with a hollow nanostructure were synthesized by a facile hydrothermal method. The structures and morphologies of the composites were investigated by different kinds of techniques，including X-ray diffraction，field-emission electron scanning microscopy，transmission electron microscopy，and energy dispersive spectroscopy. Hierarchical alpha-Fe₂O₃/NiO composites were fabricated by growing the alpha-Fe₂O₃nanorods on the surfaces of porous NiO nanosheets with a thickness of similar to 12 nm. The gas sensing properties of hierarchical alpha-Fe₂O₃/NiO composites toward toluene were investigated using a static system. The response of alpha-Fe₂O₃/NiO composites to 100 ppm toluene was similar to 18.68，which was 13.18 times higher than that of pure NiO at 300℃. The enhanced response can be attributed to heterojunction. Meanwhile，the rapid response and recovery characteristics were observed because of the porous hollow structural characteristics and catalytic actions of alpha-Fe₂O₃and NiO.