Salt-in-water and water-in-salt mixtures are promising for battery applications and fine-tuning of room-temperature ionic liquid (RTIL) properties. Although critical processes take place at interfaces of these systems, including charge transfer and heterogeneous catalytic reactions, the microscopic interfacial structures remain unclear. Here, we apply heterodyne-detected sum-frequency generation spectroscopy to aqueous solutions of imidazolium-based RTILs to unveil the microscopic structure of the interfaces of these solutions with air. Our results show that, under salt-in-water conditions, the orientation of the OH group hydrogen-bonded to the other water molecules flips from the OH group pointing down into the liquid for pure water to up due to the accumulation of anions in the cation-rich interfacial region. However, under the water-in-salt condition, the interfacial water molecules are confined by RTIL, and their orientation is down. Details of the water organization depend critically on the alkyl chain length of the imidazolium cation. Our results demonstrate that the surface structure can be tuned by altering the molecular structure and concentration of the RTIL.