Among the various possibilities offered by the periodic table, copper-rich ternary and quaternary sulfides represent a formidable source for the discovery of low cost and environmentally benign thermoelectric materials. Copper-rich sulfides form an important class where univalent copper is the dominant element, giving the possibility of creating hole carriers in the conductive “Cu–S” network for the generation of p-type thermoelectrics. During this presentation, recent advances in synthetic colusites will be shown [1-4]. Some peculiar structural features in connection with chemical bonding, such as the existence of metal complexes within the structure and/or structural disorder, were carefully examined to establish rules and correlations between the crystal structures, electronic structures, vibrational and thermoelectric properties.
 Angewandte Chemie Int. Ed. 58, 15455 (2019),  Adv. Energy Mater. 9, 1803249 (2019),  JACS 140, 2186 (2018),  PRM 4, 025404 (2020),  Chem. Mater. 32, 830 (2020),  Acta Mater. 195, 229 (2020).