Development of electrode materials for energy storage, with high energy and power densities along with good cyclic stability, still remains a big challenge. Here we report synthesis of Nb2O5/graphene nanocomposites through simple hydrothermal method, with Nb2O5 nanoparticles anchored on reduced graphene oxide (RGO) sheets. The fabricated Nb2O5/graphene electrodes exhibited excellent electrochemical performance when studied as anodes for Lithium-ion battery, with superior reversible capacity and high power capability (192 mAhg-1 under 0.1C rate over 50 cycles). Signature curve’ studies showed high power capability of Nb2O5/graphene electrode with 80% of the total capacity retained at 16C rate compared to 30% retention for pristine Nb2O5 nanoparticles. To achieve further improvement in energy density and power capability, Li-ion hybrid electrochemical capacitors (Li-HEC) are fabricated with Nb2O5/graphene nanocomposite as anode and rice husk-derived activated porous carbon as cathode, in non-aqueous electrolyte. The Li-HEC showed enhanced electrochemical performances with high energy density of 30 Whkg-1, at specific power density of 500 Wkg-1. The Nb2O5/graphene nanocomposites show promising results and hence have great potential for application in efficient electrochemical energy storage devices.