Efficient charge separation and transport as well as high light absorption are key factors that determine the efficiency of photoelectrochemical (PEC) water splitting devices. Here, a PEC device consisting of a hematite nanoporous film deposited on Pt nanopillars, followed by the decoration with an Fe₂TiO₅ passivation layer, is designed and fabricated. This structure can largely improve the light absorption in the composite materials, and significantly enhance the water oxidation performance of hematite photoanodes. The Fe₂TiO₅ thin shell and Pt underlayer significantly improve the interfacial charge transfer while minimizing the hole‐migration length in Fe₂O₃ photoanodes, leading to a drastically increased photocurrent density. Specially, the Fe₂TiO₅/Fe₂O₃/Pt photoanode yields an excellent photoresponse for PEC water splitting reactions with 1.0 and 2.4 mA cm⁻² obtained at 1.23 and 1.6 V_RHE under AM 1.5G illumination in 1 m KOH. The resulting photocurrents are 2.5 times enhanced compared to a pristine Fe₂O₃ photoanode of the same geometry. These results demonstrate a synergistic charge transfer effect of Fe₂TiO₅ and Pt layers on hematite for the improvement of PEC water oxidation.