Under conditions of excess Cu(II) ions, it is possible to synthesize a novel tetraphenylarsonium copper(II) thiocyanato anion salt, possessing the stoichiometry [AsPh4][Cu(SCN)(3)] 1. Furthermore, the crystal structure of 1 revealed the complex salt to be a rare example of a metal-thiocyanato one-dimensional chain compound, containing equatorial-equatorial copper-thiocyanato bridges. Crystal structure data (297 K) are monoclinic, P2(1)/c, a = 13.838(3) Angstrom, b = 9.679(2) Angstrom, c = 21.623(5) Angstrom, and Z = 4. Antiferromagnetic exchange through the equatorial-equatorial bridge occurs with -J = 90 cm(-1).