The outer enamel surface is of considerable interest in dentistry as it is the substrate for the acquired pellicle; the pellicle itself is the plaque carrier. In this paper the interface between outer enamel and pellicle is discussed with special emphasis on the outer enamel from a structural and chemical point of view. The outer enamel layer (less than 1 micron from the anatomical surface) is most likely a non-stoĭchiometric apatite. The chemical composition is obviously strongly different from the composition of bulk enamel. A model for the structure and atomic composition of surface enamel is presented. The available experimental evidence indicates that at an atomic scale, enamel crystallites have mainly phosphate groups (HPO42-groups) on the solid surface; the liquid adhering Stern layer contains most likely large amounts of calcium ions.