There is an increasing interest in the use of solar energy to drive the photolysis of water into molecular hydrogen by inorganic nanoparticles and photoelectrodes, which is the most ideal process to solve the energy crisis. However this reaction remains one of the biggest challenges in the photocatalysis field. Fe₂O₃ is one of the most promising materials for its application in energy and environmental fields due to its narrow band gap to absorb a large part of visible spectrum in sunlight as well as the abundant resource, the low price and environment friendliness. However, until now the reported solar-to-chemical energy conversion efficiencies of Fe₂O₃ are too low because of its ultrafast e/h recombination rate, which restrict the development of Fe₂O₃ photocatalysts. The recent progress in photocarrier separation and transport on Fe₂O₃ nano-semiconductors is reviewed in this paper. The influencing factors on the incident photo-to-current efficiency of Fe₂O₃ photocatalysts are discussed, including the heteroatom doping, the Fe₂O₃ sensitized by other semiconductors with different energy levels to form heterojunction, as well as the Fe₂O₃ with different nanostructures and nanosizes. The separation and the transport of the photo-generated electron hole pair play a pivotal role in the photoelectrocatalysis hydrogen production from water splitting on Fe₂O₃ semiconductors. A longer life of the photocarrier means a higher photocatalytic performance of Fe₂O₃. Finally, the principle, the design idea, the effects and the shortcomings of Fe₂O₃ are discussed, and the development direction of the Fe₂O₃ photocatalysts in the future is also addressed.