We have synthesized unique hierarchical one dimensional (1D) nanochains of V2O5 by employing simple hydrothermal method using cetyltrimethylammonium bromide (CTAB) as a soft template. The electrochemical performance of resulting V2O5 electrode materials was evaluated by cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance spectroscopy techniques. The V2O5 nanochains (V2O5-ctab) show maximum specific capacitance of 631 F g-1 at a current density of 0.5 A g-1 and retain 300 F g-1 even at high current density of 15 A g-1. In addition the V2O5 nanochains show good cyclic stability with 75% capacitance retention after 1200 charge-discharge cycles. The order of specific capacitance is commercial bulk-V2O5 (160 F g-1) < agglomerated V2O5 particles (395 F g-1) < V2O5 nanochains (631 F g-1). The interconnected nanochain-like morphology and high specific surface area are the main factors which contribute to higher electrochemical performance to V2O5 nanochains and promote facile exchange of Li+ ions during the charge-discharge processes. © 2016 Elsevier Inc.