Highly ordered, porous α-Fe2O3/Au nanotube arrays (NTAs) were successfully synthesized through a facile approach. Benefitting from the plasmonic effect, and unique aligned and porous structural features, the α-Fe2O3/Au NTAs offer efficient and stable operation and exhibit a significantly enhanced catalytic activity for photoelectrochemical methanol oxidation with a faradaic efficiency of 79.23%.