Supramolecular assemblies have been used largely in analytical extraction and concentration schemes. Their ability to form a phase with regions of different polarities, acidities and viscosities, where solutes of very different structure can be solubilized, has encouraged this use. At present, the basis, characteristics and scope of extraction techniques, such as cloud point, are well established. However, they have not been accepted in routine analysis, despite the demonstrated advantages of surfactant-mediated separations over other conventional extraction techniques. This article deals with the challenges in making these extraction techniques competitive and explores the potential for using other phenomena and materials where supramolecular assemblies are involved, such as coacervation, hemimicelles/admicelles and amphiphilic-templated mesoporous silicas, for the extraction/concentration of organic compounds. (C) 2003 Published by Elsevier B.V.