Decomposing water using solar energy based on photo-electrochemical process has raised wide concern as a possible means of obtaining clean and renewable hydrogen fuel. It helps relieving stress from fossil energy decrease and anthropogenic CO2 emissions to the environment. Recently, α-Fe2O3 has become a focus of photoelectrodes study due to its appropriate band gap, excellent chemical stability, abundant resource and economic feasibility. However, its poor electrical conductivity and high recombination rate of photo-generated electron/hole have restricted its development and application in photo-electrochemical water decomposition. Methods of improving performance of α-Fe2O3 photoelectrodes were summarized, including strategies of adjusting growth direction and morphology (such as multilayer films, nanotube (core-shell nanorods) and nanonet), doping with Sn, Si, Ti, Mn, Al and Zn elements, inducing oxygen vacancies and compositing with IrO2, Co-Pi, Al2O3, graphene, etc. The methods could promote transfer of photo-generated carriers, reduce probability of carrier recombination, further improve reaction photocurrent density and decrease the initiative voltage, so as to improve study of improving α-Fe2O3 performance.