Display omitted Exploring high performance cathode materials is of great means for the development of bi-functional electrochromic energy storage devices. Herein, Nb-doped WO3 mesoporous films as integrated high-quality cathode are successfully constructed via a facile sol-gel method. Chemical state and crystallinity of the WO3 based films are significantly influenced by doping concentration. Compared with the pure WO3, the optimal Nb-doped film shows improved optical-electrochemical properties with high specific capacity (74.4 mAh g−1 at 2 A g−1), excellent high-rate capability, large optical contrast (61.7% at 633 nm), and ultra-fast switching speed (3.6 s and 2.1 s for coloring and bleaching process, respectively). These positive features suggest the potential application of Nb-doped WO3 mesoporous cathode. Our research paves the way for the development of multifunctional photoelectrochemical energy devices.