Photoelectrocatalytic technology can provide an energy conservation and environmental protection way for environmental governance and chemical production. High efficient photoanodes materials are one of the challenges in the practical application of photoelectrocatalytic technique, therefore, high performance photoanode materials have been designed and developed for enhancing the application efficiency of photoelectrocatalytic technique. Fe2O3 has become a hot spot in the field of photocatalysis because of its narrow band gap, high stability and low price. In order to develop the high performance Fe2O3 photoanodes materials, many studies focused on the energy band position, conductivity and photogenerated the hole diffusion length. This review summarized the preparation techniques (hydrothermal method, spray pyrolysis, chemical vapor deposition, atomic layer deposition, etc), modification methods (“junction” construction, doping, morphological control, ect) and modified hydrogen production of the Fe2O3 photoanodes materials, the challenges and opportunities in this promising research area were proposed.