This work reports on the use of micro-Raman spectroscopy for the characterization of materials used for producing the polychrome in cultural heritage artifacts from southern Spain. The micro-Raman technique was applied for the characterization of several types of artworks or for cross-sections from these works, which were produced along different historical epochs. This technique was demonstrated to be valuable for the characterization of compounds, which were all detected within the artworks studied. The identification of all of these compounds by micro-Raman was confirmed by other complementary techniques, such as micro-X-ray diffraction and scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy.