Water-oxide surfaces are ubiquitous in nature and of widespread importance to phenomena like corrosion as well as contemporary industrial challenges such as energy production through water splitting. So far, a reasonably robust understanding of the structure of such interfaces under certain conditions has been obtained. Considerably less is known about how overlayer water modifies the inherent reactivity of oxide surfaces. Here we address this issue experimentally for rutile TiO2(110) using scanning tunneling microscopy and photoemission, with complementary density functional theory calculations. Through detailed studies of adsorbed water nanoclusters and continuous water overlayers, we determine that excess electrons in TiO2 are attracted to the top surface layer by water molecules. Measurements on methanol show similar behavior. Our results suggest that adsorbate-induced surface segregation of polarons could be a general phenomenon for technologically relevant oxide materials, with consequences for surface chemistry and the associated catalytic activity.