The solubility and the partitioning of p- and o-xylene in aqueous solutions containing M-alpha-CD, a partially methylated alpha-cyclodextrin, and the anionic surfactant sodium dodecyl sulfate (SDS) were studied by extraction experiments to evaluate the applicability of liquid membrane permeation for the separation of xylene isomeres. Experiments were carried out with the pure xylenes and 1:1 mixtures of o- and p-xylene. The interactions of M-alpha-CD and SDS and their effects on the solubility and partitioning of xylenes were investigated. M-alpha-CD was found to form 1:1 complexes with p- and o-xylene. Formation constants were determined as 141 M(-1) for p-xylene and 48 M(-1) for o-xylene, respectively, which are higher than those reported with nonmethylated alpha-CD. This can be explained by additional hydrophobic interactions with the methyl groups of the cyclodextrin. In contrast to the solubility in CD solutions, o-xylene was found to be more soluble than p-xylene in aqueous solutions of SDS. At constant concentrations of M-alpha-CD the addition of SDS led to the displacement of p-xylene from the cyclodextrin cavity, which resulted in a decrease in its solubility. This decrease lasted until micelles were formed. Due to the solubilization of p-xylene in the micelles, further addition of SDS resulted in a linear increase in the solubility of p-xylene. However, at constant CD concentrations the solubility of o-xylene increased with the addition of SDS until about 5 mmol/liter SDS. This might be attributed to the formation of a ternary complex consisting of cyclodextrin, o-xylene, and SDS. At SDS concentrations greater than 5 mmol/liter, the solubility of o-xylene decreased, which was probably due to the formation of a more stable complex between SDS and M-alpha-CD. An addition of SDS beyond a critical concentration (CMC), where micelles are formed, resulted again in a linear increase of o-xylene solubility. The CMC was found to depend linearly on the concentration of M-alpha-CD in aqueous solution. Extraction experiments with a 1:1 mixture of o- and p-xylene showed that the two xylenes and SDS are in competition for M-alpha-CD. Since surfactants are always present when using emulsion liquid membranes and due to the complex interactions between SDS, the xylenes, and M-alpha-CD, no sufficient selectivity for the separation of the xylenes by liquid membrane permeation could be achieved.