Molecular-scale structures of mica surfaces in electrolyte solutions reveal how ion and interfacial hydration control cation adsorption. Key differences are obtained for Rb+and Sr2+ using resonant anomalous x-ray reflectivity: Rb+ adsorbs in a partially hydrated state and incompletely compensates the surface charge, but Sr2+ adsorbs in both fully and partially hydrated states while achieving full charge compensation. These differences are driven by balancing the energy cost of disrupting ion and interface hydration with the electrostatic attraction between the cation and charged surface.