Coordination of Cu(I) halides with N,N′-dimethylimidazole selone (dmise) and thione (dmit) ligands was examined by treating CuX (X = Cl, Br, I) with one or two equivalents of dmise or dmit. The reaction of CuI and CuBr with one molar equivalent of dmise results in unusual selenium-bridged tetrameric Cu₄(μ-dmise)₄(μ-X)₂X₂copper complexes with average Cu–Se bond lengths of 2.42 Å and a Cu₂(μ-X)₂ core (X = I (1) or Br (6)) that’s in a rhomboidal structure. The reaction of CuX (X = Cl, Br, and I) with two equivalents of dmit or dmise results in trigonal planar Cu(I) complexes of two different conformations with the formula Cu(dmit)₂X (3a, 3b, 4, and 7) or Cu(dmise)₂X (2, 5, and 8) with average Cu–S and Cu–Se bond lengths of 2.23 Å and 2.34 Å, respectively. The coordination geometry around the copper center in complexes 1 to 8 is determined by the type of halide and chalcogenone ligand used, intramolecular π–π interactions, and short contact interactions between X–H (X = I, Br, Cl, Se or S). The theoretical DFT calculations are in good agreement with experimental X-ray structural data and indicate that dmise ligands are required for formation of the tetrameric complexes 1 and 6. Electrochemical studies show that the trigonal copper selone complexes have more negative potentials relative to analogous copper thione complexes by an average of 108 mV.