We have examined adsorption, diffusion and desorption processes of methanol on a Pt/TiO2(110) model catalyst surface by STM. Although methanol molecules were not dissociatively adsorbed on the perfect TiO2(110) terraces at room temperature, they were dissociated at Pt nanoparticles to form methoxy species, which then spilled over to the substrate 5 fold-coordinated Ti sites (Ti5c). They diffused along the [001] direction and also jumped to the next Ti5c rows, but never go over the step edge. Their density gradually decreased when the surface was stored in UHV, whose rate increased as the density of Pt nanoparticles increased.