Pureα-Fe₂O₃nanobelts (NBs) and 0.5, 1.0, 3.0 wt% reduced graphene oxide (rGO)/ α-Fe₂O₃composite nanofibers (NFs) have been successfully synthesized by a homotaxial electrospinning method. Various techniques were employed for the characterization of the nanostructures and morphologies of the as obtained nanofibers. The results indicate that pure α-Fe₂O₃NBs have uniform widths more than 200 nm and series of rGO/α-Fe₂O₃NFs have diameters approximately 100 nm. In addition, the gas sensing properties of the obtained nanofibers were investigated. It is found that 1 wt% rGO/α-Fe₂O₃shows high response, excellent repeatability and long-term stability to 100 ppm acetone at the operating temperature of 375 ℃. The response of 1 wt% rGO/α-Fe₂O₃nanofibers to 100 ppm acetone is about 8.9, which is about 4.5 times higher than pure α-Fe₂O₃NBs. Furthermore, the combination of rGO with α-Fe₂O₃can also improve the response/recovery properties. The response and recovery times of the sensor were about 3 and 9s, respectively, which were superior to pure α-Fe₂O₃NBs. Finally, we have proposed that the creation of ohmic contact, defects on the rGO nanosheets surface play significant roles in raising the sensitivity of rGO/α-Fe₂O₃NFs.