Arrayed porous iron-doped TiO(2) with controllable pore size was prepared by using polystyrene spheres and its structure, morphology, composition and photoelectrochemical properties were characterized with X-ray diffraction, scanning electron microscope, inductively coupled plasma-atomic emission spectrometer and electrochemical methods. It is found that the photoelectrochemical properties of the arrayed porous TiO(2) can be improved by doping adequate amount of iron in the lattice of TiO(2) and the sample doped with 0.01 wt% Fe (based on Ti) exhibits the best photoelectrochemical performance. With doping 0.01 wt% Fe in TiO(2), the photocurrent density of the sample is improved from 2.0 mu A cm(-2) to 10.0 mu A cm(-2) and its flat-band potential shifts from -0.38 V to -0.55 V (vs. SCE). Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.