Laser-induced autofluorescence spectra of teeth irradiated by a 337 nm nitrogen laser were measured during in vitro caries formation through initial enamel demineralization and introducing of carious bacterial flora in the lesions developed. Spectra obtained from sound teeth consist of an intensive maximum at 480-500 nm and secondary maximum at 430-450 nm. In the process of caries formation, we observed an increase in the intensity at 430-450 nm and the appearance of two maxima in the red spectral region-at 590-650 nm. The intensity increase at 430-450 nm was related to the tooth demineralization. Bacteria presence and their metabolism products induced an increase in the absorption in the UV-blue spectral region at 350-420 nm and the appearance of a fluorescence signal in the long-wave spectral region at 590-650 nm. From the point of view of tissue optics, these results allow caries to be considered as consisting of two different phenomena-tissue destruction and bacterial flora and its metabolism products increase. The results could be used to obtain a more complete picture of caries formation on the base of its fluorescent properties.