The balance of the charge transfer and recombination kinetics of photoelectrodes governs the device efficiency for solar water splitting. Hematite (α-Fe₂O₃) is a photoanode typically used because of advantages such as its abundance, low cost, multiple convenient deposition methods, and an attractive bandgap energy; however, poor electrical properties prevent high solar energy to hydrogen conversion efficiencies. In this work, we evaluate and compare several strategies to address this issue, using a nanorod array morphology and incorporation of overlayers of one or more materials that favor the charge carrier transfer kinetics and reduce surface recombination. We use intensity-modulated photocurrent spectroscopy (IMPS) to evaluate these systems, and demonstrate that the presence of TiO₂ and MoO _x overlayers successfully suppresses surface recombination through passivation of hematite interfacial recombination sites. However, the hole transfer process at the overlayers occurs at more positive potentials due to the location of the new surface states at the overlayer—electrolyte interface. We show that the deposition of the CoP_i oxygen evolution reaction co-catalyst partially addresses this disadvantage. The best efficiencies were obtained for the CoP_i-TiO₂/α−Fe₂O₃ and CoP_i-MoO _x /TiO₂/α−Fe₂O₃ photoelectrodes, with internal quantum efficiencies of 0.42−0.44 under 455 nm irradiation.