The detection of the beginning demineralization process of dental hard tissue remains a challenging task in dentistry. As an alternative to bitewing radiographs, optical and spectroscopic technologies showed promising results for caries diagnosis. The aim of the present work is to give an overview of optical and spectroscopic properties of healthy and carious human teeth in vitro by means of Raman spectroscopy (RS), optical coherence tomography (OCT) and hyperspectral imaging (HSI). OCT was able to represent microstructural changes below the enamel surface and revealed increased scattering for white spot lesions and a white scattering trail for deeper lesions. HSI showed similar absorbance characteristics for healthy and demineralized enamel over the entire spectrum and a characteristic absorbance peak at 550 nm for discolored lesions. Already at early carious stages (white spot), we found a distinct loss of hydroxylapatite-related intensity at 959 cm^-1 in demineralized regions with RS. Healthy and demineralized tooth surfaces can be distinguished at different signal levels by means of RS, OCT and HSI. The presented modalities provide additional information to the current clinical diagnosis of caries such as microstructural changes, quantification of the demineralization and imaging of caries-related chemical changes.