Different effects of support hydrophilicity and metal-oxide on the performance of Pt-based catalysts were investigated with the aim of improving the mass activities toward methanol electrooxidation. Both potentiodynamic and potentiostatic measurements revealed that improved surface hydrophilicity of multi-wall carbon nanotubes (MWCNTs) could promote the dispersion of Pt nanoparticles and, consequently, promote the Pt utilization and reduce the polarization in methanol electrooxidation. In addition, WO 3 was shown to play a supportive role in enhancing catalytic activity. The interaction between Pt and WO 3 was examined by CO-stripping and CO oxidation transient experiments. The results suggested that the activity and the kinetics of monolayer CO ads electrooxidation of Pt nanoparticles are enhanced by the adjacent WO 3 via a bifunctional mechanism, which accounts for improved activity in methanol electrooxidation.