While orthorhombic niobium pentoxide (T-Nb2O5) is one of the most promising energy storage material with rapid lithium ion (Li+) intercalation pseudocapacitive response, a key challenge remains the achievement of high-rate charge-transfer reaction when fabricated into thick electrodes. Herein, we report a facile method to create intrinsic defects in T-Nb2O5 through a hydrogen (H-2) reduction, which is effective to overcome the limitations of electrochemical utilization and rate capability. Due to the high number of active sites introduced, the specific capacity of hydrogenated (H-) Nb2O5 with oxygen vacancies reaches 649 C g(-1) at 0.5 A g(-1), greatly exceeding that of T-Nb2O5 which is 580 C g(-1). In addition, the formation of oxygen vacancies leads to increased donor density and enhanced electrical conductivity, which accelerates charge storage kinetics and enables excellent long-term cycling stability (86% retention after 2000 cycles). The analysis of electrochemical impedance spectroscopy (EIS) plots and the calculation of Li+ diffusion coefficients (D-Li) further explains the high rate-performance of H-Nb2O5. When the electrode thickness increased to 150 mu m, the H-Nb2O5 still delivers excellent electrochemical properties. Therefore, the introduction of oxygen vacancies provides a new method towards the improvement of the electrochemical properties of various transition metal oxides. (C) 2019 Elsevier Inc. All rights reserved.