In this study, we report for the first time the synthesis of nickel titanate (NTO) nanofibers containing a mixture of ilmenite and spinel phases of NTO, at an atypical low temperature. Precursor nanofibers produced by sol-gel electrospinning were calcined at three different temperatures to produce the NTO nanofibers. Thermal analysis along with X-ray photoelectron spectroscopy confirmed the formation of non-crystalline stable phases of TiN and Ti-O-N that restrained the formation of ilmenite NTO, and the Ni-rich environment pushed the Ti atoms to tetrahedral sites to form a defective spinel structure. The crystallite size of spinel NTO was observed to increase as a function of the calcination temperature above 700 degrees C, as the activation energy for coalescence and growth of spinel NTO was favorable. NTO nanofibers obtained above the calcination temperature of 700 degrees C exhibited new band gap energy around 2.5 eV in Tauc plot. Oxygen vacancies in these ceramic nanofibers decreased as the calcination temperature was increased. A hypsochromic shift of 20 nm in the photoluminescence spectra suggested that the material had a Ni2+ rich NTO (spinel).