A simple method for the large-scale synthesis of SnO₂ nanofibers has been demonstrated through an electrospinning method. The as-synthesized fibers are characterized by scanning electron microscopy, transmission electron microscopy, selected area electron diffraction, X-ray diffraction, and energy dispersive X-ray analysis. The sensor fabricated from these fibers exhibits high response to toluene at 350 °C with good selectivity. The response time and recovery time are about 1 and 5 s, respectively. The linear dependence of the response value on the toluene concentration is observed in the range of 10–300 ppm. The potential application of SnO₂ nanofibers for fabricating high performance toluene sensors at industry level has been demonstrated.