Pure and 0.18-13.2 at.% Fe-doped NiO nanofibers were prepared by electrospinning and their gas sensing characteristics and microstructural evolution were investigated. The responses ((Rg - Ra)/Ra, where Rg is the resistance in gas and Ra is the resistance in air) to 5 ppm C2H5OH, toluene, benzene, p-xylene, HCHO, CO, H2, and NH3 at 350-500 ° C were significantly enhanced by Fe doping of the NiO nanofibers, while the responses of pure NiO nanofibers to all the analyte gases were very low ((Rg - Ra)/Ra = 0.07-0.78). In particular, the response to 100 ppm C2H5OH was enhanced up to 217.86 times by doping of NiO nanofibers with 3.04 at.% Fe. The variation in the gas response was closely dependent upon changes in the base resistance of the sensors in air. The enhanced gas response of Fe-doped NiO nanofibers was explained in relation to electronic sensitization, that is, the increase in the chemoresistive variation due to the decrease in the hole concentration induced by Fe doping.