The highly ordered titanium dioxide nanotube array (HOTDNA) electrodes were prepared in hydrofluoric acid solution by electrochemical anodic oxidation technique on a pure titanium sheet. The HOTDNA electrodes were characterized by X-ray diffraction, SEM microscopy, and UV-vis spectra. It has shown high density, well ordered and uniform titanium dioxide nanotube array film covered on these electrodes and the TiO2 structure depending on the heating condition, the anatase phase of TiO2 appeared when heating to 500 degrees C. The photoelectrochemical characteristics of methanol in 0.5 M Na2SO4 on the HOTDNA electrodes were investigated. The cyclic voltammetry, photocurrent-time and open-circuit photopotential response of methanol on the HOTDNA electrode were represented and significant photogenerated current was observed upon illumination in the UV regions with the light of 253.7 nm central wavelength. The effect of variables such as light intensity, applied potential, and methanol concentration on the photoelectrochemical response was investigated. It was found that the photocurrent was greatly influenced by these factors. (c) 2007 Elsevier B.V. All rights reserved.