T-Nb2O5/reduced graphene oxide nanohybrids were fabricated via the hydrothermal attachment of Nb2O5 nanowires to dispersed graphene oxide nanosheets followed by a high-temperature phase transformation. Electrochemical measurements showed that the nanohybrid anodes possessed enhanced reversible capacity and superior cycling stability compared to those of a pristine T-Nb2O5 nanowire electrode. Owing to the strong bonds between graphene nanosheets and T-Nb2O5 nanowires, the nanohybrids achieved an initial capacity of 227 mAh.g(-1). Additionally, non-aqueous asymmetric supercapacitors (ASCs) were fabricated with the synthesized nanohybrids as the anode and activated carbon as the cathode. The 3 V Li-ion ASC with a LiPF6-based organic electrolyte achieved an energy density of 45.1 Wh.kg(-1) at 715.2 W.kg(-1). The working potential could be further enhanced to 4 V when a polymer ionogel separator (PVDF-HFP/LiTFSI/EMIMBF4) and formulated ionic liquid electrolyte were employed. Such a quasi-solid state ASC could operate at 60 degrees C and delivered a maximum energy density of 70 Wh.kg(-1) at 1 kW.kg(-1).