We have investigated hydroxylation and water adsorption on a-Fe2O3(0001) at water vapor pressures up to 2 Torr and temperatures ranging from 277 to 647 K (relative humidity (RH) less <= 34%) using ambient-pressure X-ray photo electron spectroscopy (XPS). Hydroxylation occurs at the very low RH of 1 10^-7 % and precedes the adsorption of molecular water. With increasing RH, the OH coverage increases up to one monolayer (ML) without any distinct threshold pressure. Depth profiling measurements showed that hydroxylation occurs only at the topmost surface under our experimental conditions. The onset of molecular water adsorption varies from ~2 10^-5 to ~4 10^-2 % RH depending on sample temperature and water vapor pressure. The coverage of water reaches 1 ML at ~15% RH and increases to 1.5 ML at 34% RH. Show Partial Abstract