The spontaneous emulsification of alcoholic solutions of trans-anethole (t-A) in water is investigated using EXSY and DOSY NMR techniques. The system investigated (5-10 mM t-A in 5% EtOH/H2O solution) is exceptional in providing sharp, clearly resolved signals for both t-A that is dissolved in the aqueous phase (free t-A) and t-A that is incorporated in aggregates (3-6 nm diameter) thus allowing both fractions to be probed simultaneously. This feature is utilized to explore the initial events that occur during the spontaneous emulsification process. Upon mixing, the majority of the t-A (ca. 75%) undergoes nucleation to form small aggregates (ca. 10 nm diameter), while 15% (corresponding to [t-A] = 7.5 x 10(-4) M) is dissolved in the aqueous phase. The kinetic rates governing the exchange process between aggregated and free t-A are found to be time-dependent and slow on the NMR time scale (k = 0.8-2 s(-1)). DOSY experiments indicate that the initially formed small aggregates undergo rapid coalescence to form larger droplets. Ostwald ripening of these droplets at the expense of the remaining small aggregates is responsible for the subsequent, slower time-evolution of the system.