Evenly dispersed Pt–Ni nanoparticles were loaded on TiO 2 nanotube arrays (TiO 2 NTs) via pulse electrodeposition method and subsequently characterized by FESEM, EDX and XRD. The electrochemical studies showed that the catalytic activities of Pt–Ni/TiO 2 NTs are better than that of Pt/TiO 2 NTs for methanol electro-oxidation in alkaline media both in the dark and under illumination. In addition, due to the interaction of electro-catalysis and photo-catalysis, the catalytic activities of TiO 2 NTs-based catalysts were improved largely under illumination. Base on the results obtained in this work, Pt–Ni/TiO 2 NTs may be used to develop a base for photo assist direct methanol fuel cell.