The self-association of n-hexyltrimethylammonium bromide (C(6)TAB) in aqueous solution has been examined as a function of temperature and electrolyte concentration. The critical micelle concentration (CMC) and the degree of counterion binding (beta) were determined by conductivity measurement at temperatures over the range 288.15-318.15 K. Ultrasound velocity measurements were used to obtain the CMC in water and in a range of concentrations of electrolyte (0.1 to 0.6 mol kg(-1) NaBr) and static light scattering to obtain the aggregation number and the degree of counterion binding in water at 298.15 K. The enthalpy change on micellization in water was measured by microcalorimetry, Apparent adiabatic compressibilities were calculated from a combination of density and ultrasound velocity measurements. Changes in the thermodynamic properties on micellization were determined by applying the mass action model; good agreement was found between experimental and theoretical enthalpy changes. From comparison with the properties of other n-alkyltrimethylammonium bromides it has been shown that the CMC of C(6)TAB in water is lower than that predicted from the linear relationships between CMC and the number of carbon atoms in the alkyl chain. Similarly, the standard Gibbs energy of micellization is less negative than predicted, and the degree of counterion binding is much lower than for other C(n)TABs. It is suggested that the anomalous behavior of C(6)TAB is a consequence of the more highly organized core of the aggregates of very low aggregation number (3-4) and the high degree of exposure of the micellar components to the aqueous environment.