Oxides are most commonly found in divided forms with properties difficult to control since their crystallographic orientations usually escape analysis. To overcome this an appropriate model system can be provided by ZnO smoke which, obtained by combustion of Zn in air, exhibits nanoparticles with well-defined surface facets. The present work focuses on the interaction of water with ZnO smokes by combining density functional theory based simulations and infrared spectroscopy measurements with applied pressures from 10(-7) to 1 mbar. We demonstrate that the use of ultra-high vacuum allows the analysis of the very first stages of the adsorption, and report on water structures on ZnO(11 (2) over bar0) for the first time. We further show that ZnO powders behave as multi-facet single crystals involving (10 (1) over bar 10), (11 (2) over bar0), (0001), and (000 (1) over bar) surfaces with the polar orientations corresponding to 25% of the total surface area. A great deal of cross-agreements between experimental results and simulation provides a simple approach for the examination of hydroxylated/hydrated ZnO smokes and can be widely applied on other ZnO-related powders.