Linker molecules are added to microemulsion systems to enhance the interaction between the surfactant and oil (lipophilic linkers) or water (hydrophilic linkers) phases. Previous results suggest that when lipophilic and hydrophilic linkers are combined they behave as a self-assembled surfactant at the oil/water interface. In this work we investigate this self-assembly phenomenon as a function of surfactant, linker and electrolyte concentration. We find that middle phase microemulsion appears at a specific concentration higher than the critical micelle concentration (CMC), which we denote as the critical middle phase microemulsion concentration (CmuC). When the lipophilic linker dodecanol is added in equimolar ratio to the hydrophilic linker sodium mono- and dimethyl naphthalene sulfonate (SMDNS), the middle phase microemulsion did not appear until the surfactant sodium dihexyl sulfosuccinate (SDHS) concentration was larger than the CmuC of the SDHS-alone system. Dodecanol is shown to segregate near the surfactant tails following a Langmuir-type adsorption process. This segregation is not affected by the electrolyte concentration but is significantly reduced when the surfactant (SDHS) concentration approaches the CmuC. The data suggest that the self-assembly between hydrophilic and lipophilic linkers to form middle phase microemulsions is only possible if a minimum amount of surfactant is present. (C) 2004 Elsevier Inc. All rights reserved.