Clay minerals are used in variety of applications ranging from composites to electronic devices. For their efficient use in such areas, understanding the effect of surface-active agents on interfacial properties is essential. We investigated the role of surface ions in the adsorption of water molecules by using a muscovite mica surface populated with two different, H(+) and K(+), surface ions. A series of grand canonical Monte Carlo (GCMC) simulations at various relative vapor pressures (p/p0) were performed to obtain the water structure and adsorption isotherm on the H(+)-exposed mica (H-mica) surface. The obtained results were compared to the recent simulation data of water adsorption on the K(+)-exposed mica (K-mica) surface reported by Malani and Ayyappa (Malani, A.; Ayappa, K. G. J. Phys. Chem. B 2009, 113, 1058-1067). Water molecules formed two prominent layers adjacent to the H-mica surface, whereas molecular layering was observed adjacent to the K-mica surface. The adsorption isotherm of water on the K-mica surface was characterized by three stages that corresponded to rapid adsorption in the initial regime below p/p0 = 0.1, followed by a linear development regime for p/p0 = 0.1-0.7 and rapid film thickening for p/p0 ≥ 0.7, whereas only latter two regimes were observed in the H-mica system. In addition, the film thickness of adsorbed water molecules for p/p0 < 0.7 was lower as compared to that for the K-mica surface and comparable beyond. The film thickness obtained from the MC simulations was in excellent agreement with the interferometry experimental data of Balmer et al. (Balmer, T. E.; Christenson, H. K.; Spencer, N. D.; Heuberger, M. Langmuir 2008, 24, 1566-1569). It was observed that the hydration behaviors of the two ions were completely different and depended on the size of their hydration shell and their ability to form hydrogen bonds. The behavior of water adsorption between these two cases was illustrated using the water density distribution, orientational distributions, hydrogen bonding, and isosteric heats of adsorption.