Stannous fluoride but not stannous chloride has shown a caries inhibiting effect in animal studies. The effect of aqueous solutions of stannous fluoride and stannous chloride on dental enamel surfaces was investigated by scanning electron microscope and analytical electron microprobe. Some large globules and a continuous layer of small globules were observed after stannous fluoride treatment. The large globules were soluble in both water and alkali, whereas the small ones were only soluble in alkali. Both fluoride and tin were found to be present on the enamel surfaces by the electron microprobe after stannous fluoride treatment. The fluoride could not be detected after immersion in distilled water whereas alkali treatment removed the tin. The large fluoride-containing globules may consist of calcium fluoride as this substance is known to be slightly soluble in water and soluble in alkali. Stannous chloride treatment gave a layer of small tin-containing globules with properties similar to the layer formed on enamel treated with stannous fluoride. It is therefore suggested that the tin-containing layer is not associated with caries protection whereas calcium fluoride-like deposition on the enamel probably is a factor in the caries inhibition caused by stannous fluoride.