Given its peculiar crystal structure and inherent surface charge, the (001) plane of muscovite mica has served as an excellent model system to study the hydration and electric double layer (EDL) forces at solid-liquid interfaces [1]. So far, force spectroscopies, which measure along the direction perpendicular to the surface, as well as molecular dynamics (MD) simulations, have demonstrated a certain ionspecificity towards the strength of hydration forces on mica surfaces [2-5]. These deviations are mainly attributed to the different properties of individual ions (e.g., hydration shell, size, valency, etc.), which ultimately determine their adsorption character on mica, as well as the interfacial hydration structure [5]. Nevertheless, lateral distribution and arrangement of cations adsorbed on mica was experimentally investigated only to a lesser extent [6], although unravelling the ions’ organisation directly at the surface is crucial to elucidate the structure and properties of EDLs. In the present contribution, we discuss how high-resolution atomic force microscopy (AFM) imaging enables us to visualize the lateral distribution of individual mono- and multi-valent ions on the surface of mica. Thanks to this approach, we are able not only to resolve the crystal structure of mica immersed in aqueous solution, but also to transiently picture the population of adsorbed ions from the salt-rich solutions at different concentrations. By using an automated triangulation algorithm, the ion adsorption coverage as a function of concentration can be quantified in a first order approximation. This methodology highlights the possibility to outline a certain competitive behaviour of charged species at the surface. Understanding such competition as a function of type and concentration of ions allows us to unravel the interfacial thermodynamics directly from AFM data, which has been so far mainly exclusive to MD simulations. To further support our findings, we use surface force apparatus and MD simulations to characterischaracterise the structure and mechanical properties of EDLs on mica for different cation species