The coadsorption of methanol (CH3OH) and water (D2O) on the MgO(100)/Mo(100) surface at 100 K has been studied by metastable impact electron spectroscopy (MIES), ultraviolet photoelectron spectroscopy [UPS (HeI)], and by thermal programmed desorption (TPD). Methanol wets the MgO surface and adsorbs nondissociatively within the first monolayer with the hydroxyl group oriented toward the substrate. In coadsorption experiments, methanol wets a water precovered MgO surface; however, adding water to a methanol precovered MgO surface does not yield a water-only surface. Essentially, a constant fraction of the preadsorbed methanol remains within the topmost surface layer during the buildup of the water multilayer. Temperature-dependent measurements show that the adsorption and desorption dynamics of both water and methanol are governed by intermolecular interactions rather than adsorbate-substrate interactions.