Porous TiO2 thin films were prepared on the Si substrate by hydrothermal method, and used as the Pt electrocatalyst support for methanol oxidation study. Well-dispersed Pt nanoparticles with a particle size of 5-7 nm were pulse-electrodeposited on the porous TiO2 support, which was mainly composed of the anatase phase after an annealing at 600 °C in vacuum. Cyclic voltammetry (CV) and CO stripping measurements showed that the Pt/TiO2 electrode had a high electrocatalytic activity toward methanol oxidation and an excellent CO tolerance. The excellent electrocatalytic performance of the electrode is ascribed to the synergistic effect of Pt nanoparticles and the porous TiO2 support on CO oxidation. The strong electronic interaction between Pt and the TiO2 support may modify CO chemisorption properties on Pt nanoparticles, thereby facilitating CO oxidation on Pt nanoparticles via the bifunctional mechanism and thus improving the electrocatalytic activity of the Pt catalyst toward methanol oxidation.