SnO2/Al2O3 nanofibers have been fabricated from a suitable inorganic–organic composite solution via a simple electrospinning method and followed by calcination treatment of the electrospun polymer/inorganic composite fibers. The effect of voltage, tip-to-collector distance and calcining temperature on the morphology and crystal structure of nanofibres was investigated by scanning electron microscope (SEM), X-ray photoelectron spectra (XPS) and X-ray diffraction (XRD). The diameter and diameter distribution of nanofibers can be controlled by controlling the electrospinning parameters and the more ideal diameter is 200-350nm. The formation of phase identified by XRD indicated the existence of tetragonal rutile tin oxide crystals and amorphous alumina. This paper provides a new method for the preparation of the SnO2/Al2O3 catalysts for NOX reduction.