Self-assembly in aqueous solutions of cationic surfactants that carry thioether groups in their hydrophobic tails has been investigated. Of particular interest was the identification of possible changes in the aggregate structure due to the presence of sulfur atoms. Solutions of four different compounds [CH3CH2S(CH2)(10)N(CH3)(3)Br-+(-) (2 - 10), CH3(CH2)(5)S(CH2)(6)N(CH3)(3)Br-+(-) (6 - 6), CH3(CH2)(7)S(CH2)(6)N(CH3)(3)Br-+(-) (8 - 6), and CH3(CH2)(7)S(CH2)(8)N(CH3)(3)Br-+(-) (8 - 8)] were characterized by H-1 NMR, C-13 NMR, NMR diffusometry, and conductivity measurements. In addition to investigating aqueous solutions containing each of the thioethers present as the sole solute, mixtures of 2 - 10 or 6 - 6 with dodecyltrimethylammonium bromide (DTAB) were studied. The addition of a sulfide group to the hydrophobic tail causes an increase in the critical micelle concentration but has a limited effect on the aggregate structure. Micelles are formed at a well-defined concentration for all of the investigated surfactants and surfactant mixtures. However, a comparison of the behavior of concentrated solutions of 8 - 8 to that of solutions of hexadecyltrimethylammonium bromide (CTAB) of similar concentrations suggests that the presence of a sulfur atom decreases the tendency for micellar growth. This may be a consequence of a slightly higher preference for the micellar Surface of a sulfur atom as compared to that of a methylene group in a similar position, an idea that is also supported by results for the surfactant mixtures.