To explore the photoelectrochemical efficiency of hematite as a photoanode, we comprehensively investigate the electronic structures of hematite doped with 4d transition-metal X (X = Y, Zr, Mo, Tc, Rh, and Ru) based on the density-functional theory (DFT). The results indicate that the bandgap of hematite can be reduced by doping with the transition metal atoms, which leads to the enhanced absorption coefficient of long-wavelength photons in the visible light region. In addition, the carrier concentration can be improved by Zr, Mo, Tc, and Ru dopants. More interesting, the incorporation of Ru can also modify the conduction band edge and hence reduce the effective electron mass, leading to better electron mobility. Subsequent experiments confirm that the photoelectrochemical (PEC) activity of Ru doped hematite film is significantly improved. For example, the highest photocurrent density value of 9 at.% Ru doped hematite is 4.7 times that of the undoped material at E = 1.23 V. Based on both calculations and experiments, the enhanced PEC activities of Ru doped hematite are derived from the improved electrical conductivity and increased visible light absorption coefficient.