In the present work, a simple, scalable and cost - effective synthesis approach has been used for preparation of V 2 O 5 powder by thermal decomposition method. Firstly, the physicochemical properties such as XRD, FESEM, contact angle, BET etc., of V 2 O 5 powder annealed at 400 0C, 500 0C, and 600 0C (denoted as V1, V2, and V3 respectively) were studied. Subsequently followed by a detailed investigation of the electrochemical properties. The electrochemical properties of active V 2 O 5 –Ni foam (VNF) electrode showed pseudocapacitive nature. The V1–NF electrode exhibits highest specific capacitance of 1227.2 F g-1 as compared with V2–NF (723.8 F g-1) and V3–NF (511.2 F g-1) at the scan rate of 1 mV s-1 in 1 M KOH aqueous electrolyte with three-electrode system. The optimum electrode showed specific capacitance retention of approximately 96.1 %, even after 2000 consecutive GCD cycles. Therefore, VNF is the promising electrode material for supercapacitor application. [Display omitted] • Nano-structured V2O5 prepared by simple and scalable thermal decomposition method. • Effect of annealing temperature on physicochemical and electrochemical properties is examined. • Fabricated V1– NF electrode exhibit specific capacitances 1227.2 F g-1 at the scan rate 1 mV s-1. • V2O5 is the promising material for supercapacitor application. [ABSTRACT FROM AUTHOR]