The title compound, [Cu 4 (C 9 H 11 ) 4 (C 3 H 9 P) 2 ] or [Cu 4 (Mes) 4 (PMe 3 ) 2 ] (Mes = 2,4,6-trimethylphenyl), was synthesized from copper(I) mesityl and trimethylphosphane in THF as solvent. The molecular structure of the complex has C 2 symmetry and consists of four copper(I) atoms bridged by four μ -mesityl groups, giving an eight-membered puckered {Cu 4 C 4 } ring. Additionally, two copper(I) atoms at opposite corners of the Cu 4 rhomb are each linked to a terminal PMe 3 ligand. The PMe 3 -bearing copper(I) atoms exhibit a distorted trigonal–planar coordination mode whereas the remaining Cu atoms linked to two mesityl groups are nearly linearly coordinated.