Alkyloxyethylene sulfates are a special class of surfactants that are unusually stable in the presence of multivalent counterions and are not as prone to precipitation as anionic surfactants without intermediate ethoxy groups in the molecule. However, formation of micelles, their structure, and the properties of monolayers of these surfactants exhibit very interesting and sometimes unexpected properties depending on the nature of the ions dissolved in the solution. This paper presents a brief overview of our recent efforts to reveal the nature of these properties, including some new results. We show that the strong binding of multivalent (and particularly trivalent counterions) triggers a sphere-to-cylinder shape transition of the micelles and facilitates their further growth, even at very low ionic strength. The properties of surfactant monolayers are coupled to those of the micelles in the bulk and are governed also by multivalent counterion binding. The effect of multivallent counterions on the aggregation and structure formation in anionic surfactant solutions has both fundamental and practical importance. (C) 2003 Elsevier Science (USA). All rights reserved.