Carious lesion presents chemical and structural modification. For better diagnosis of early carious, and to detect carious therapeutic and preventive efficiency, several optical methods have been proposed and developed. Based on Raman scattering effect, Raman spectroscopy has the features of good reproducibility, high sensitivity and quantitative analysis, and it has been gradually considered in caries research as a noninvasive testing technique. This review focused on the principle and characteristics of Raman spectroscopy and its application in detecting early caries, evaluating the efficiency of chemo-mechanical caries removal and composite adhesive restoration, as well as studying caries-preventive mechanisms of laser and caries-preventive effect of fluoride.