The photooxidation of methanol as a model substance for pollutants on rutile TiO 2 (001) and (100) surfaces was investigated using intensity modulated photocurrent spectroscopy (IMPS). The results are analyzed in view of the influence of the surface structure, the methanol concentration and the electrode potential on the rate constants of charge transfer and recombination. The obtained results have been explained with a model combining the theory of IMPS for a bulk semiconductor surface and the nature of the surface-bound intermediates (alternatively mobile or immobile OH radicals). The results indicate that water photooxidation proceeds via mobile OH radicals on both surfaces, while methanol addition gives rise to the involvement of immobile OH radicals on the (100) surface. Detailed analysis in view of the surface structures suggests that the latter observation is due to efficient electron transfer from bridging OH radicals on the (100) surface to methanol, while coupling of two of these radicals occurs in the absence of methanol, making them appear as mobile OH radicals. In the case of the (001) surface, the coupling reaction dominates even in the presence of methanol due to the smaller distance between the bridging OH radicals, leading to more efficient water oxidation, but less efficient methanol photooxidation on this surface. © the Owner Societies 2012.