Substitutional doping can improve the electronic properties of α-Fe2O3 for the solar photoelectrochemical PEC) applications. Generally speaking, nonisovalent substitutional doping helps to enhance the electronic conductivity of α-Fe2O3. However, we found that the introduction of strain in the lattice, which is achieved by isovalent substitutional doping of an Al, can also improve the electronic properties. α-Fe2O3 films with the Al dopant atomic concentration varying from 0 to 10% were prepared by electrodeposition, and their performance for photoelectrochemical hydrogen production was characterized. Results indicate that the incident photon conversion efficiency (IPCE) for ∼0.45 at-% Al substitution increases by 2- to 3-fold over undoped samples. Density-functional theory (DFT) was utilized to interpret the experimental findings. It was shown that although no substantial change to the electronic structure, a contraction of the crystal lattice due to the isovalent replacement Of Fe3+ by an Al3+ benefits the small polaron migration, resulting in an improvement in conductivity compared to the undoped samples.