In this paper, nanofibers composed of spinel Li4Ti5-xFexO12 (x = 0 and 0.1)/carbon were synthetized by electrospinning method. Thermal analysis of the prepared fiber was conducted by differential thermal/thermogravimetric analysis, crystal structure was characterized by X-ray diffraction, morphology and composition was determined by scanning electron and transmission electron microscopy. The results showed that fibers were composed of nanocrystals of lithium titanate with an average diameter from 17 to 25 nm supported in a carbonaceous matrix. The added Fe played an important role in improving the electronic conductivity and the charge-transfer process of the Li4Ti4.9Fe0.1O12/C electrode. Due to the morphological and structural features of these novel nanostructured materials, it can be considered as promising candidates for applications in lithium ion batteries.