A brief introduction to Optical Coherence Tomography (OCT) is presented, stressing the origin of the tomographic signal and the detection methods defining various modalities of the technique. The parameters of the tomographs, such as axial and lateral resolution, wavelength and intensity of the probing light, imaging range, time of examination, and sensitivity are then defined, and a paradigm for interpreting the OCT tomograms provided. The second part of the article comprises a review of the utilisation of OCT for structural examination of artworks, illustrated with some representative results. Applications to the structural imaging of semi-transparent subsurface layers such as varnishes and glazes, of underdrawings and of reverse painting on glass, are described first, and then applications in the examination of the structure and state of preservation of historic glass, jade, glazed porcelain and faience are discussed. Finally, the use of OCT combined with LIBS analysis and laser ablation of surface layers is presented.