Titania/titanium (TiO2/Ti) electrodes with tailored surface structure have been fabricated by galvanostatic-potentiostatic anodization process. Highly ordered titania nanotubes array can be prepared by electrolyzing titanium foil at 20 V for 40 min in HF-H3PO4 electrolyte. Comparatively, micro-structured and crystallized TiO2 multiporous film can be prepared at 20-40 V for 6 h in H2SO4-H3PO4-H2O2-HF electrolyte. The morphological characteristics and crystal behaviors of both nanotubular and micro-structured TiO2 films are investigated by field emission scanning electron microscopy and X-ray diffraction measurement. Photoelectrochemical properties of TiO2/Ti film electrodes are examined by anodic photocurrent response and cyclic voltammetry measurement. Photocatalytic and photoelectrocatalytic application are investigated by using either nanotubular TiO2/Ti thin-film or micro-structured TiO2/Ti thick-film electrodes as photoanodes for recalcitrant organic pollutant degradation. (c) 2005 Elsevier Ltd. All rights reserved.