Quantitative X-ray fluorescence imaging of sections of human teeth revealed an increased concentration of copper and zinc in carious regions of dentine compared with unaffected portions of the tooth. Higher-resolution images provided strong evidence that the copper was transported and localized mainly in the dentinal tubules. While similar levels of zinc were found in these areas and concentrated in the tubules, zinc was also more evident in the hydroxyapatite, and the increase in zinc levels compared with the levels in background (normal) areas was less than that for copper. These results suggest a role for copper and zinc in the formation and progression of dental caries and present a potential point of intervention for treatment.