Using a unique three-solvent biphasic method, we have prepared and characterized three new fully conjugated, chalcogen-rich, bridged copper(II) complexes for the preparation of molecular conductors and magnetic materials, having the general formula (Bu(4)N)(2){tto[Cu(L)](2)} (tto = C2S42- = tetrathiooxalato; L = mnt = C4N2S22- = 1,2-dicyanoethene-1,2-dithiolato for complex 2, dsit = C3Se2S32- = 2-thioxo-1,3-dithiole-4,5-diselenolato for complex 3, dmid = C3OS42- = 2-oxo-1,3-dithiole-4,5-dithiolato for complex 4a). The single-crystal X-ray structures of 2 and 3 have been determined : 2, (Bu(4)N)(2){tto[Cu(mnt)](2)}, monoclinic, space group C2/m, a 19.549(4) Angstrom, b = 13.519(3) Angstrom, c = 10.162(2) Angstrom, beta = 90.33(1)degrees, Z= 2; 3, (Bu(4)N)2{tto[Cu(dsit)](2)}, monoclinic, space group P2(1)/c, a = 9.903(1) Angstrom, b = 15.589(1) Angstrom, c = 18.218(1) Angstrom, beta = 90.40(1)degrees, Z = 2. Complex 2 displays perfect planarity, while 3 shows a slight tetrahedral distortion at the metal centers, resulting in a dihedral angle of 24.86(3)degrees. Cyclic voltammetry of (Bu(4)N)(2){tto[Cu(mnt)](2)} (2), (Bu(4)N)(2){tto[Cu(dsit)](2)} (3), and (Bu(4)N)(2){tto[Cu(dmid)](2)} (4a) shows each complex to exhibit two reversible redox processes which can be attributed to {tto[Cu(L)](2)}(2-) reversible arrow tto[Cu(L)](2)}(-) and (tto[Cu(L)](2))(1-) reversible arrow {tto[Cu(L)](2)}(0) couples. The structural and electronic properties of 2, 3, and 4a will be compared to those of the recently communicated analogous complex (Bu(4)N)(2){tto[Cu(dmit)](2)} (1).