To develop anode catalysts for photo-assisted direct methanol fuel cell (PDMFC), carbon-doped TiO2 nanotube arrays-supported PtNi alloy nanoparticles with different Pt/Ni atomic ratio (PtNi/C-TiO2NTs) prepared by pulsed electrodeposition method are evaluated as catalysts for photo-assisted methanol oxidation. The cyclic voltammetry (CV) and chronoamperometry results show that the PtNi/C-TiO2NTs prepared at t(onPt):t(onNi) := 10:7 (t(on) is the current-on time) with a Pt:Ni atomic ratio of 6.1:5.7 presents the highest catalytic activity for methanol oxidation both in the dark and under illumination. In addition, according to the results obtained from the CO stripping voltammetry and electrochemical impedance spectroscopy (EIS) tests, it was found that the light play an accelerative role in the oxidation of methanol on PtNi/C-(TiONTs)-N-2 under illumination. The effect of illumination which enhancing the catalytic activity of PtNi/C-TiO2NTs are attributed to (1) methanol and the intermediates be oxidized directly on C-TiO2NTs for the light-induced catalytic effect; (2) more abundant oxygen-donating species be produced on C-TiO2NTs in the presence of light; (3) less COads adsorbing on catalysts due to the presence of stronger metal support interactions between PtNi alloy nanoparticles and C-TiO2NTs under illumination. (C) 2012 Elsevier Ltd. All rights reserved.