Room-temperature ionic liquids (ILs) exhibit a unique set of properties, leading to opportunities for numerous applications. To obtain a better understanding of IL interfaces at a molecular level, we combined charged surfactants with ILs and studied their interfacial behavior. The critical micelle concentration (cmc) of each surfactant IL pair was determined from both solubility phase diagrams and isotherms. Because the cmc is equivalent to the solubility at the Krafft temperature:, a connection between the solubility of the surfactant and the physical properties of the underlying ionic liquid was established. Interfacial energy was found to be the major factor affecting the surfactant aggregation process, although its magnitude depends strongly on the IL structure. The results here give insight into explaining the nature of self-assembly of surfactants at IL interfaces and the interaction between solutes and IL solvents.