Pureα-Fe₂O₃nanotubes and a series of Al₂O₃/α-Fe₂O₃composite nanofibers were synthesized via facile electrospinning and subsequent calcination at 500℃ in air for 2 h. The morphologies and nanostructures of these samples were characterized through various experimental techniques. It was found that the composite samples were composed of crystal alpha-Fe2O3 and amorphous Al2O3. The composite Al₂O₃/α-Fe₂O₃nanofibers have smaller grain size than that of pure Al₂O₃/α-Fe₂O₃nanotubes prepared by the same process. Furthermore, comparative gas sensing investigation between Al₂O₃/α-Fe₂O₃composite nanofibers and pureα-Fe2O3 nanotubes was performed to show the superior sensing properties of the composite samples. When the mass ratio of Al source and Fe source was 1:4, the sensor exhibited the highest response to 100 ppm triethylamine at 250℃. It is worth noting that the response times were no more than 2 s at operating temperatures ranged from 175 ℃ to 300 ℃. Finally, the related mechanism of gas sensing and the role of Al₂O₃in the composite nanofibers were discussed in this paper.