Nanofibers (NFs) of Ga-doped ZnO (GZO) were prepared by electrospinning of polymer–salts solution. Sintering profiles reported in the literature led to loss of the fibrous structure. Hence, the morphology, thermal stability, and phase composition of green and sintered fibers were investigated as function of sintering conditions to elucidate this degradation process. Optimal results were obtained at 400 °C for 30 min. This low temperature sintering of GZO fibers has not been previously reported. The fibers were porous with a significant surface area, making it possible to test their sensitivity to environmental changes. In particular, the response of the GZO NFs to changes in humidity was demonstrated for the first time. The electrical and sensing properties of single NFs prepared at these conditions were studied using a field-effect transistor mode.