Condensation and arrangement of ions at water-solid interfaces are of great importance in the formation of electrical double layers (EDL) and the transport of ions under a confined geometry. So far, the microscopic understanding of interfacial ion configurations is still far from complete, especially when the local ion concentration is high and ion-ion interactions become prominent. In this study, we directly visualized alkali metal cations within the hydrogen-bonding network of water on graphite and Cu(111)-supported graphene surfaces, using qPlus-based noncontact atomic force microscopy (NC-AFM). We found that the codeposition of the alkali cations and water molecules on the hydrophobic graphite surface leads to the formation of an ion-doped bilayer hexagonal ice (BHI) structure, where the ions are repelled from each other and scattered in a disordered distribution. In contrast, the hydrated alkali cations aggregate in one dimension on the more hydrophilic graphene/Cu(111) surface, forming a nematic state with a long-range order. Such a nematic state arises from the delicate interplay between water-ion and water-water interactions under surface confinement. These results reveal the high sensitivity of ion-ion interactions and ionic ordering to the surface hydrophobicity and hydrophilicity.