For many years after the discovery of its caries preventive effect, fluoride was thought to be primarily active by lowering the solubility of the apatitic mineral phase of the dental hard tissues. Recent findings have shed new light on the mechanisms by which fluoride inhibits or delays dental caries. Fluoride present in the oral fluids alters the rate of the naturally occurring dissolution and reprecipitation processes at the tooth-oral fluid interface. Demineralization of enamel is inhibited by concentrations of fluoride in the sub-ppm range. Likewise, remineralization of incipient caries lesions (the earliest stage of enamel caries) is accelerated by trace amounts of fluoride. As these two processes comprise dental caries the physiological balance between hard tissue breakdown and repair is favorably shifted by fluoride. The driving force for both phenomena is thermodynamic, that is, fluorapatite or a fluoridated hydroxyapatite may form when fluoride is supplied at low concentrations. This article critically reviews the current information about tooth-fluoride interactions, both from laboratory and clinical studies.