ABSTRACT The mineral thorikosite Pb3(OH)(SbO3,AsO3)Cl2 is named after the ancient city of Thorikos, in the region of Attica, where the ancient mine sites dating back to the bronze ages are found. Raman spectra of the antimonite-bearing mineral thorikosite Pb3(OH)(SbO3,AsO3)Cl2 were studied and were related to the structure of the mineral. Two intense Raman peaks were observed at 596 and 730 cm−1 and were assigned to the Sb3+O3 and As3+O3 stretching vibrations. A peak at 1085 cm−1 is assigned to the Sb3+OH deformation mode. Raman band at 325 cm−1 is assigned to an OAsO bending vibration of the As3+O3 units, and the bands at 269 and 275 cm−1 are attributed to the OSbO bending modes of the Sb3+O3 units. The intense Raman bands at 112 and 133 cm−1 are associated with PbCl stretching modes. Minerals such as nealite and thorikosite are minerals of archaeological significance. Yet no spectroscopic studies of these minerals had been undertaken.