Solar hydrogen conversion via photoelectrochemical water splitting is an important technology for energy and environment sustainability. Since the pioneering work of Fujishima and Honda in 1972, tremendous research on semiconductor-based photoelectrochemical water splitting has yielded better understanding of the processes as well as encouraging development of high efficiency photoelectrodes for solar hydrogen generation. Given the narrow band gap enabling excellent optical absorption, increased charge carrier density and accelerated surface oxidation reaction kinetics become the key points for improved photoelectrochemical performances for water splitting over α-Fe₂O₃ photoanodes. In this talk, some recent progresses in surface modified α-Fe₂O₃ for photoelectrochemical solar water splitting in our group will be introduced. By engineering the surface structures of α-Fe₂O₃ nanorods with Ag_xFe_2-xO₃, TiO₂ and HfO₂ overlayers, the surface charge recombination was greatly inhibited and the surface water oxidation kinetics were efficiently accelerated, resulting in remarkable enhancement in PEC water splitting performances.