The title compound has been synthesized by the reaction of sodium α-dithionaphthoatewith CuCl_2 in an alkaline aqueous solution or by the reaction of α-dithionaphthoic acid withCuCl_2 in an organic solvent, The crude product was recrystallized in a mixture of CS_2 andC_2H_5OH. The crystals obtained are red and stable in air. The structure of the title compound is determined by a single-crystal X-ray diffractionanalysis. The crystal belongs to monoclinic space group C_(2h)~5- P(2_1/a) with unit cell parameters:a= 16.453(3)A, b=12.651(4)A, c=23.182(7)A, β=100.5(2)°, V=4744.6A~3,Z=4. Thestructure was refined to R=0.06 for 4707 reflections. In the molecule, Cu_4 cluster has a distorted tetrahedral configuration. Surrounding thistetrahydron are four α-perthionaphthoate ligands, coordinated to copper through the sulfuratoms. One of the sulfur atoms in each ligand forms sulfur bridge with copper atoms,while the other is coordinated to only one copper. The three Cu--S bonds formed by thethree sulfur atoms with a given copper atom are approximately coplanar. Each group--C--S_2 with Cu atom on a vertex of the tetetrahedron forms a five-member ring. Thesefive-member rings are also approximately cooplanar. The molecule possesses an approachingS_4 point symmetry. The mechanism for the formation of the title compound involves a redox reaction.which is discussed in this paper. The title compound has been synthesized by the reaction of sodium α-dithionaphthoate with CuCl_2 in an alkaline aqueous solution or by the reaction of α-dithionaphthoic acid with CuCl_2 in an organic solvent, The crude product was recrystallized in a mixture of CS_2 and C_2H_5OH. are red and stable in air. The structure of the title compound is determined by a single-crystal X-ray diffraction analysis. The crystal belongs to monoclinic space group C_ (2h) ~ 5- P (2_1 / a) with unit cell parameters: a = 16.453 (3) A, b = 12.651 (4) A, c = 23.182 (7) A, β = 100.5 (2) °, V = 4744.6A -3, Z = 4. The structure was refined to R = 0.06 for 4707 reflections. In the molecule, Cu_4 cluster has a distorted tetrahedral configuration. Surrounding this tetrabutylammonium are four α-perthionaphthoate ligands, coordinated to copper through the sulfuratoms. One of the sulfur atoms in each ligand forms sulfur bridge with copper atoms, while the other is coordinated to only one copper. The three Cu - S bonds formed by thet Each group - C - S_2 with Cu atom on a vertex of the tetetrahedron forms a five-member ring. Thesefive-member rings are also approximately cooplanar. The molecule possesses an approachingS_4 point symmetry. The mechanism for the formation of the title compound involves a redox reaction.which is discussed in this paper.