Vanadium pentoxide (V2O5) thin layers were hydrothermally deposited on self-standing carbon nanofibre (CNF) paper, which was fabricated through electrospinning of polyacrylonitrile (PAN) precursor solution followed by thermal stabilization and carbonization. The prepared V2O5/CNF nanocomposite paper was characterized by various spectroscopic and microscopic techniques. The electrochemical performance of as-prepared free-standing nanocomposite electrode was examined using cyclic voltammetry (CV) and galvanostatic charge-discharge techniques for supercapacitor applications. A specific capacitance of 227 F/g and 157 F/g were achieved for the nanocomposite obtained from V2O5-deposition of 5 and 7-day period, respectively, using 2 M KCl as electrolyte at sweep rate 1 A/g. The specific capacitance of the nanocomposites was retained up to 80% over 1000 cycles. The maximum energy density of 63.6 Wh/kg and power density of 4554.6 W/kg was achieved for the 5-day deposited samples. A simple and cost-effective synthesis approach of flexible binder-free V2O5/CNF nanocomposite paper with good capacitive behavior encourages its commercial exploitation. (C) 2016 Published by Elsevier Ltd.