The stable oil-in-water microemulsions with a high water content were formed on the basis of cationic surfactants, including those that contain a hydroxyalkyl fragment in the head group. These systems can bind the water-and oil-soluble reagents into a single aggregate formed by self-assembling components. The size, surface and electrokinetic potentials of aggregates in the surfactant/n-hexane/n-butanol/water microemulsions were determined. Besides, their catalytic effect on the cleavage of carboxylic acid esters was evaluated. The behavior of the system was shown to be determined not only by hydrophobic and electrostatic interactions but also by specific interactions, i.e., hydrogen bonds. (C) 2013 Elsevier B. V. All rights reserved.