The fluoride content of the enamel and dentine of premolars was used as a determinant of the availability of ingested fluoride in New Zealand prior to and following the introduction of water fluoridation 40 years ago. Premolar teeth, which developed during the periods (PRE and POST respectively) under study, were selected from teeth extracted from 12 to 14-year-old children resident in different geographic areas in the country. The fluoride content, determined by multiple proton microprobe analyses, of surface enamel, deep enamel, and dentine, were for PRE teeth 440, 65 and 115, respectively. For POST teeth the mean values were significantly (p < 0.001) higher, by 69, 29 and 102% respectively. The relevance of the change in fluoride content was assessed by comparison with published reports on the fluoride content of teeth developed in communities exposed to low ( < 0.5 ppm), optimal (1–2 ppm) and high ( > 3 ppm) naturally occurring fluoride levels in drinking water. The PRE teeth had a fluoride content associated with a low fluoride exposure and POST teeth with optimal fluoride exposure during tooth development. It was concluded that fluoride availability in New Zealand teeth had increased over the past 30 years but this increase is compatible with exposure of the community to optimal rather than excessive levels of ingested fluoride.