Ni nanoparticles were loaded on TiO2 nanotube arrays (Ni/TiO2NTs) via pulsed electrodeposition method and employed as catalyst for methanol oxidation in alkaline media. The as-prepared Ni/TiO2NTs catalyst was characterized by field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and electrochemical analyzer. The electrochemical studies showed that Ni/TiO2NTs under illumination exhibited higher catalytic activity and stronger poisoning-tolerance for methanol oxidation than that in the dark. The effect of illumination which improved catalytic activity of Ni/TiO2NTs were attributed to the p-n junction formed at the interface between Ni(OH)(2) and TiO2NTs resulting in the photo-generated holes flow into Ni(OH)(2), thus, the transmitted holes boosted the oxidation of Ni(OH)(2) and produced the OH- to oxidize methanol and intermediates that absorbed on the catalyst. The present study shows Ni/TiO2NTs can act as a promising candidate for the anode catalyst in photo assist direct methanol fuel cells (PDMFCs) application. Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.