The interaction of water with freshly cleaved BaF2 (111) surfaces has been studied using scanning force microscopy operated in different modes at room temperature and under controlled humidity. The Kelvin probe microscopy (KPM) mode has been used to study the evolution of the surface potential differences (SPDs). In the 20%-50% relative humidity (RH) range, adsorbed water forms two-dimensional solidlike bilayers (islands). The SPD between water islands and the bare substrate surface exhibits a sign crossover from negative (∼-30 mV) at low RHs to positive (∼+50 mV) at higher RHs, evidencing a cooperative and irreversible flipping of the preferential orientation of water dipoles, from pointing toward the surface evolving into the opposite direction. The KPM results suggest that the classical hexagonal (Ih) bilayer configuration is not the most favorable structure. © 2008 American Institute of Physics.