This study demonstrates the highly enhanced photocatalytic activity of Fe₂O₃ nanotubes by making a heterojunction with Fe₂WO₆ and doping of W⁶⁺ ions into the α-Fe₂O₃ phase for water splitting and decomposition of an organic pollutant. Both nanotubular and compact Fe₂O₃/Fe₂WO₆ films are formed by anodizing the magnetron-sputtered Fe-9 at% W alloy in fluoride-containing ethylene glycol electrolyte and subsequent annealing at 450 °C. Their photocatalytic activities are compared with W-free nanoporous Fe₂O₃ film formed on high-purity Fe. The nanotubular Fe₂O₃/Fe₂WO₆ film exhibits a markedly enhanced photoelectrochemical oxygen evolution reaction and photocatalytic degradation of methylene blue compared with the nanoporous W-free Fe₂O₃ film. Because of the larger surface area, the nanotubular Fe₂O₃/Fe₂WO₆ film reveals further increased activity than the compact Fe₂O₃/Fe₂WO₆ film. The STEM study discloses the dispersion of Fe₂WO₆ nanoparticles in the α-Fe₂O₃ phase after annealing at 450 °C, and XRD analysis shows the possible doping of W species into α-Fe₂O₃. The formation of the W-doped α-Fe₂O₃/Fe₂WO₆ heterojunction likely promotes the separation of photogenerated electron-hole pairs, enhancing photocatalytic activity. Hence, the nanotubular Fe₂O₃/Fe₂WO₆ film is a possible candidate for visible-light-driven photocatalysts.