A series of mixtures comprising Imwitor 742 and Tween 80 have been prepared and their self-emulsifying properties studied using a method of visual examination. The particle size distributions of emulsions prepared from these mixtures at 25°C, 37°C in water and 37°C in 0.1 M HCl have been measured. A marked decrease in mean particle size was observed for 30 and 40% Imwitor 742/Tween 80 mixtures at 25°C with a decrease in particle size also being noted for the majority of Imwitor 742/Tween 80 compositions at higher temperatures. Low frequency dielectric spectroscopy was performed on the pure components and on binary systems to which water had been added to make 50% v/v mixtures. Evidence was shown for the formation of liquid crystalline phases at concentrations corresponding to those shown to be efficient self-emulsifying systems. The study therefore suggests that self-emulsification may be associated with liquid crystal formation and that low frequency dielectric spectroscopy may be of considerable use in understanding the factors leading to self-emulsification.