Incipient dental caries lesions appear as white spots on the tooth surface; however, accurate detection of early approximal lesions is difficult due to limited sensitivity of dental radiography and other traditional diagnostic tools. A new fibre-optic coupled spectroscopic method based on polarized Raman spectroscopy (P-RS) with near-IR laser excitation is introduced which provides contrast for detecting and characterizing incipient caries. Changes in polarized Raman spectra are observed in PO4 3- vibrations arising from hydroxyapatite of mineralized tooth tissue. Demineralization-induced morphological/orientational alteration of enamel crystallites is believed to be responsible for the reduction of Raman polarization anisotropy observed in the polarized Raman spectra of caries lesions. Supporting evidence obtained by polarized Raman spectral imaging is presented. A specially designed fibre-optic coupled setup for simultaneous measurement of parallel- and cross-polarized tooth Raman spectra is demonstrated in this study.