Thin water films that form by the adhesion and condensation of air moisture on minerals can initiate phase transformation reactions with broad implications in nature and technology. We here show important effects of water film coverages on reaction rates and products during the transformation of periclase (MgO) nanocubes to brucite [Mg(OH)2] nanosheets. Using vibrational spectroscopy, we found that the first minutes to hours of Mg(OH)2 growth followed first-order kinetics, with rates scaling with water loadings. Growth was tightly linked to periclase surface hydration and to the formation of a brucite precursor solid, akin to poorly stacked/dislocated nanosheets. These nanosheets were the predominant forms of Mg(OH)2 growth in the 2D-like hydration environments of sub-monolayer water films, which formed below ∼50% relative humidity (RH). From molecular simulations, we infer that reactions may have been facilitated near surface defects where sub-monolayer films preferentially accumulated. In contrast, the 3D-like hydration environment of multilayered water films promoted brucite nanoparticle formation by enhancing Mg(OH)2 nanosheet growth and stacking rates and yields. From the structural similarity of periclase and brucite to other metal (hydr)oxide minerals, this concept of contrasting nanosheet growth should even be applicable for explaining water film-driven mineralogical transformations on other related nanominerals.