Interactions of CH3OH with stoichiometric (nearly defect-free) and defective TiO2(110) and (100) surfaces have been studied using x-ray photoelectron spectroscopy and ultraviolet photoemission spectroscopy. The CH3OH saturation coverage was increased by increasing the number of defects created by electron-beam exposure or Ar+ ion bombardment. A small percentage of any defects produced were healed upon the saturation exposure (defect healing means a reduction in defect signal observed by the photoemission measurements). The structural influence on the adsorption and surface defect reactivity was found to be less significant for CH3OH than for H2O. The CH3OH coverages at a given exposure and defect reactivity were comparable for both the (100) and (110) surfaces.