Unraveling the catalytic functionality of hydrophilic surfaces from a molecular level is of a great challenge, but it offers fundamental guidelines for mechanistic understanding of the heterogeneous catalysis and eventually facilitates the development of highly efficient catalysts. Here, we present a combined experimental and theoretical study of hydroxylated monomeric vanadia species deposited on the θ-Al2O3(010) surface and the subsequent dissociative adsorption of methanol. First, the structure of a hydroxylated θ-Al2O3(010) surface with one monolayer of water coverage is generated. Energies associated with the dissociative adsorption of water indicate that hydroxylation is a strongly exothermic process. The normalized intensities of the vibrational modes of the in situ IR spectra of θ-Al2O3 as a function of temperature show that the hydrated θ-Al2O3(010) surface gradually dehydrates with increase in temperature up to 300 °C, which agrees well with a previous theoretical calculation and shows the prese...