In this work we demonstrate the suitability of confocal Raman microscopy for the characterisation of carious dental tissues. Samples of enamel and dentine, presenting carious lesions in different stages of progression, were evaluated by comparing the depolarisation ratio of the PO43– symmetric stretching band at 959 cm–1 in the different tissues. Both line and area scans were performed to gauge these variations. Moreover, the obtained results were compared with the tissues’ behaviour when interacting with ultraviolet radiation, namely the induced fluorescence in some tissues. The depolarisation ratio has proven to be a valuable tool in recognition of demineralisation of both enamel and dentine due to caries. The analyses of the collagen bands in the dentine sample turned out to be more difficult to evaluate due to high fluorescence in the carious region.