Reaction of these salts with [Cu(PPh 3 ) 3 Cl] gave a series of organotetrel-copper chalcogenide clusters [(CuPPh 3 ) 6 (PhTE 3 ) 2 ] with T/E = Si/S; (5), Si/Se (6), Sn/S (7) and Sn/Se (8).Compounds 5-8 share a common structural motif with two intact {PhTE 3 } units coordinating a Cu 6 moiety, which was previously reported with other ligands, and for the Sn and Ge congeners only. If the Sn/Se reaction system was allowed to crystallize more slowly, single crystals of compound [(CuPPh 3 ) 6 (PhSnSe 3 ) 3 Cu 3 SnSe] (9) were obtained, which are based on a larger cluster structure. Hence, 9 might form from 8 through incorporation of additional cluster fragments. The experimentally and quantum chemically determined optical properties were compared to related clusters.