Various vanadium oxide nanostructures are currently drawn interest for the potential applications of Li batteries, super capacitors, and electrochromic display devices. In this article, the synthesis of V2O5 nanotubes by hydrothermal method using 1-hexadecylamine (HDA) and PEO as a template and surface reactant were reported, respectively. The structural properties and electrochemical performances of these nanostructures were investigated for the application of Li batteries. Structure and morphology of the samples were investigated by XRD, FTIR, SEM, and TEM analysis. The battery with V2O5 nanotubes electrode showed initial specific capacity of 185 mAhg(-1), whereas the PEO surfactant V2O5 nanotubes exhibited 142 mAhg(-1). It was found that PEO surfactant V2O5 nanotubes material showed less specific capacity at initial stages but better stability was exhibited at higher cycle numbers when compared to that of V2O5 nanotubes. The cyclic performance of the PEO surfactant material seems to be improved with the role of polymeric component due to its surface reaction with V2O5 nanotubes during the hydrothermal process.