The present paper reviews the applications of Raman spectroscopy in dentistry in the past two decades. This technique is considered a highly promising optical modality, widely used for the chemical identification and characterization of molecular structures, providing detailed information on the structural arrangement, crystal orientations, phase, and polymorphism, molecular interactions and effects of bonding, chemical surrounding environment, and stress on samples. Raman spectroscopy has been appropriate to investigate both organic and inorganic components of dental tissues since it provides accurate and precise spectral information on present minerals through the observation of the characteristic energies of their vibrational modes. This method is becoming progressively important in biomedical research, especially for non-invasiveness, non-destructiveness, high biochemical specificity, low water sensitivity, simplicity in analyzing spectral parameters, near-infrared region capability, and in vivo remote potential by means of fiber-optics. This paper will address the application of Raman spectroscopy in different fields of dentistry, found to be the most relevant and prevalent: early recognition of carious lesions; bleaching products performance; demineralizing effect from low-pH foods and acidic beverages; and efficiency of remineralization agents. Additionally, this review includes information on fiber-optic remote probe measurements. All described studies concern caries detection, enamel characterization, and assessment indicating how and to what extent Raman spectroscopy can be applied as a complementary diagnostic method.