The retention of KOH-soluble and structurally bound fluoride in dentin after topical application of aminefluoride was investigated. One cylindrical dentin sample was prepared from each of 40 extracted third molars. All samples received one topical application of 1 microL of aminefluoride solution (1.23% F) for three min. Ten of them were analyzed immediately after fluoridation. The remaining 30 samples were mounted in the buccal aspects of a special mouth application which was carried by a person for five days. After one, three, and five days, 10 of the 30 samples were removed from the appliance. In all samples, the amount of structurally bound fluoride was determined in three layers (20 microns, 20 microns, 20 microns) by use of a special grinding technique. Before each grinding step, the dentin specimens were analyzed for KOH-soluble fluoride. The total amount of KOH-soluble fluoride in dentin was 48.7 +/- 14 micrograms/cm2. It decreased drastically during the experimental period. Structurally-bound fluoride increased one day after fluoridation in the first and second layers. Thus, topical application of aminefluoride resulted in a significant accumulation of KOH-soluble fluoride in dentin. This precipitate was unstable, but fluoride ions released from it could perhaps increase the amount of structurally bound fluoride.