AbstractThe preparation, some spectral properties and the crystal structure of a compound of composition [Cu2Au(Bu2dtc)6][Hg2Br6]*, are reported. The crystal structure is isomorphous with the tricopper analogue: [Cu3(Bu2dtc)6][Cd2Br6].X‐Ray data for the present compound are: space group Pī; unit cell:a= 12.614(4),b= 13.691(4),c= 12.502(4) Å, α = 96.37(4)°, β = 91.47(4)°, γ = 85.43(4)°, with one formula unit per cell. Atomic parameters were refined to a conventionalR‐value of 0.056 for 1752 independent non‐zero reflections. The structure consists of two ionic units: [Cu2Au(Bu2dtc)6]2+and [Hg2Br6]2–. Thenon‐centriccation is situated at a centrosymmetric position, with disordered Cu(III) and Au(III) attached to a central Cu(II) atom.This central Cu(II) atom has an apically distorted octahedral S‐coordination, with Cu–S distances of 2.33(1), 2.28(1), and 3.20(1) Å. The disordered [Cu(III), Au(III)] positions have five‐fold pyramidal S‐coordination with distances of 2.25(1), 2.26(1), 2.29