The amount of alcohol required to produce a microemulsion in a quaternary water-in-oil system was evaluated for a series of alcohols and hydrocarbon solvents of different size or topology. It was observed that the amount of n-hexanol and n-decanol required was similar in all the solvents considered. On the other hand, considerably higher concentrations of the branched alcohols (2,4-dimethyl-3-pentanol and 3-ethyl-3-pentanol) were required to produce the microemulsion, irrespective of the solvent topology (n-hexane or 2,2,4-trimethylpentane). From an analysis of the change in the analytical alcohol concentration with the surfactant concentration the amounts of alcohol present at the microaggregates' surface at the point of microemulsion formation were obtained. It is concluded that the high amounts of branched alcohols required are due to both less efficient incorporation at the interface and the larger number of alcohol molecules per surfactant required to stabilize the microemulsion. (C) 2004 Elsevier Inc. All rights reserved.