Charged materials in aqueous systems interact according to their interfacial properties, typically described by the electrical double layer (EDL). Distributions or divalent metal cations at the muscovite (001)-solution interlace observed using resonant anomalous X-ray reflectivity demonstrate an unexpected complexity with respect to the EDL structure. Three forms of adsorbed cations can coexist: the classical inner-sphere and outer-sphere complexes and a third "extended" outer-sphere complex located farther from the surface. Their relative proportions are controlled by the energy balance among cation hydration, interface hydration, and electrostatic attraction. Systematic trends in coverage and position establish the defining role of cation hydration in stabilizing the multiple coexisting species.