The aggregation characteristics of tetraethylammonium perfluorooctylsulfonate in water were studied by several techniques: conductivity, pH, ion-selective electrodes, and surface tension. It was concluded that the aggregation process is gradual and starts with the formation of oligomers such as ion pairs that grow to give spherical micelles, which become wormlike with increasing concentration. Because of the size and hydrophobicity of the counterion, micelles quickly increase in ionization degree up to about 0.5. Differences among different critical micelle concentration values in the literature are explained on the basis of the gradual formation of micelles. (c) 2005 Elsevier Inc. All rights reserved.