The gossamer-like Nb2O5-RGO nanocomposite was synthesized through a solvothermal treatment, and the Nb2O5 nanoparticles were uniformly coated on the RGO sheets. The size of the Nb2O5 nanoparticles is about 200–700 nm. The applications of Nb2O5-RGO as supercapacitor were then explored systematically. The morphology, textural structure, and physicochemical property of Nb2O5-RGO were investigated by using SEM, TEM, XRD, FT-IR, TG, and Raman. The electrochemical performance of RGO, Nb2O5, and Nb2O5-RGO was assessed through CV and galvanostatic charge-discharge test. The experimental results show that gossamer-like Nb2O5-RGO exhibits partial faradic pseudocapacitance and good electrical double layer capacitance property. The specific capacitance value 299.23 Fg−1 of Nb2O5-RGO nanocomposite is about 2.7 and 1.7 times higher than that of Nb2O5 and RGO, retaining 87.72% of its initial capacitance after 2000 cycles under the optimized conditions, which demonstrate that more ordered binary architecture Nb2O5-RGO nanocomposite along with easy synthesis possesses faster charge-discharge kinetics and excellent supercapacitive performance.