We studied spectral autofluorescence characteristics of dental caries. A wide range of carious lesions revealed characteristic emission of endogenous fluorophores with strong fluorescence bands in the red spectral region when excited with 407 nm line radiation of a krypton ion laser. Healthy hard dental tissue exhibited no emission bands in the red. The fluorescence spectra, fluorescence excitation spectra as well as the reflectance spectra of carious lesions were found to be typical for fluorescent porphyrins, mainly protoporphyrin IX. A possible source of these porphyrins within carious tissues is bacterial biosynthesis. Non-invasive sensitive in vivo caries detection by means of appropriate excitation sources and porphyrin fluorescence detectors should be possible.