We found that a rutile single-crystalline TiO2(1 0 0) surface exhibits "biphased" structure in air that consists of structurally and chemically different domains. We observed their structural evolution caused by thermal annealing at 900 degrees C by the contact mode of atomic force microscopy (AFM) and investigated their chemical properties by frictional mode AFM, which can be used to estimate local hydrophilicity of the surface. The two domains are distinguished by their morphological height and hydrophilicity, the latter of which is determined by the density of hydroxyl groups. The structural evolution and the final domain arrangement upon annealing are influenced by the initial atomic step arrangement before the annealing. We also demonstrated that a self-assembled monolayer of the silane-coupling agent is selectively formed only on the hydrophilic domains and that photochemical reaction using ultraviolet light eliminates the chemically characterized biphase feature. (C) 2014 Elsevier B.V. All rights reserved.