This contribution describes the synthesis of a hybrid nanocomposite constituted by vanadium oxide/polyaniline (PANI) with an interesting fibrilar morphology. Nanofibers can be obtained as main reaction products of nanocomposite V2O5/PANI and hexadecylamine after hydrothermal treatment. In general, nanocomposite nanofibers present a typical length varying from 1 to 10μm and a width varying from 15 to 300nm. Electrochemical experiments have shown a specific capacity of about 150Ahkg−1 during the 10 initials cycles. The apparent diffusion coefficient has evaluated by electrochemical impedance spectroscopy. The value obtained for nanofibers with template was approximately 1×10−12 cm2/s−1. On the other hand, nanofibers passed by a reflux treatment, were hexadecylamine was changed by sodium cations presented an apparent diffusion coefficient at least three orders in magnitude higher than the parent “with template”, comparable with other vanadium oxide described in the literature, revealing a promissory material for utilization as cathode for ion-Li batteries.