Titanium dioxide (TiO2) and titanate materials such as nanotubes, nanobelts and nanorods were synthesized and their co-catalytic effects were studied by mixing them with Pt/C catalysts. After mixing with these nanomaterials, the methanol oxidation current of Pt/C was increased significantly, but ethanol oxidation current of Pt/C was not increased in acidic medium. Combining with material characterization and electrochemical measurements, the result showed that the co-catalysts with suitable porous channels and higher proton conductivity could accelerate the methanol oxidation, and the co-catalysts containing more adsorbed and structural water could better increase the oxidation of intermediates. TiO2(B) nanobelts and titanate nanotubes are newly developed nanomaterials and protons could transfer along their long-axis. They have showed good co-catalytic effect and would have more applications in direct alcohol fuel cells (DAFC).