Nuclear magnetic resonance line-widths of23Na have been determined at several compositions in two isotropic solution phases and five mesomorphous phases in the sodium caprylate-decanol-water system. The results obtained demonstrate that the rate of nuclear magnetic relaxation of23Na+ is primarily determined by the number of water molecules per sodium ion. this indicates that in all the phases investigated, the sodium ions are predominantly coupled to water molecules. A comparison with81Br nuclear magnetic relaxation data shows that the bonding of sodium ions is markedly different from that of bromide ions in systems containing association colloids and water. This diversity is found to be due to differences in ion-water coupling.