The potential of micellar cloud point systems for extraction processes has been demonstrated for a broad range of different applications. The extraction is based on the phenomenon that aqueous non-ionic surfactant solutions split into two phases if the temperature is increased beyond a certain temperature, the so called cloud point temperature (CPT). Recently, aqueous micellar two-phase systems have been implemented in a counter current extraction. However, almost equally important for large scale applications is the recovery of the solute from micellar solutions, which remains a serious concern considering micellar cloud point systems as alternative to conventional solvents. In conventional solvent extraction processes the influence of the pH on the partitioning of ionizable solutes is an important parameter to control the extraction and back extraction efficiency. However, the partitioning of ionizable solutes such as organic acids and bases in micellar two-phase systems has not been studied so far. In this work the partitioning of various ionizable solutes including phenolic as well as pharmaceutical active compounds has been investigated. Lipophilicity profiles of all solutes were analyzed for the system Triton X-114/water in a pH range between 2 and 12. Further, the influence of temperature, solute concentration, as well as different salt concentrations on the partitioning of charged solutes was investigated. Experimental results are verified by means of predicted values using the thermodynamic model COSMO-RS. The results reveal that COSMO-RS can be applied to predict the partitioning of ionizable solutes in micellar biphasic systems, when the phase behavior of the pure surfactant is known. Based on these data optimal strategies for large scale micellar extraction processes are proposed and validated by means of a continuous pilot plant micellar extraction column. (C) 2012 Elsevier B.V. All rights reserved.