A diagnostic technique to detect residual tissues at different levels of the root canal during an endodontic treatment is presented. The diagnostic system is based on ultraviolet-induced fluorescence spectroscopy and uses suitable optical fibers for local delivery of excitation light and to collect back fluorescence spectra. Spectra of root canal tissues have been obtained from split teeth by labeling with a fluorescent solution. Residual tissue can be discriminated in respect to healthy dentin because of their different spectral responses: the spectral shape of the first response shows a clear peak at 530 nm because of a selective absorption of the fluorescent dye, whereas for the second response, the spectral curve monotonically increases toward ultraviolet wave-lengths with no particular structure. This technique has been tested on unsplit teeth simulating operative conditions. A compact spectroscopic system has been devised that can be easily integrated in an excimer laser system to perform residual tissue detection during laser cleaning of the canals.