In this study, the band structure of In2O3/N–InNbO4 composite was considered to be advantageous for the transportation and separation of photoexcited electron/hole pairs. This composite was synthesized and characterized by powder x-ray diffraction, UV-visible diffuse reflectance spectroscopy, transmission electron microscope, and x-ray photoelectrons spectroscopy. The photocatalytic experiments indicated the H2 evolution rate of In2O3/N–InNbO4 composite was 27.3 μmol h−1 g−1 under visible light irradiation (λ>420 nm), which was 18.6 times the rate of In2O3 and 2.3 times the rate of N–InNbO4.