In the crystal structure of the title compound, K(4)[Au(4)Ni(2)(C(6)H(8)NO(4)S)(C(5)H(9)NO(2)S)(4)(C(5)H(10)NO(2)S)].C(2)H(6)O.10H(2)O, (I), two planar [Ni(C(5)H(9)NO(2)S)(2)](2-) units are spanned by [Au(2)(C(5)H(10)NO(2)S)](+) and [Au(2)(C(6)H(8)NO(4)S)](-) linkers through S atoms, forming an S:S-bridged Au(I)(4)Ni(II)(2) hexanuclear complex anion. One of six organic ligands in the complex anion is a carbamino derivative of D-penicillamine (3-mercaptovaline) and the others are deprotonated D-penicillamines. Each complex anion binds to nine K(+) ions through six carboxylate and one carbamino groups to construct a three-dimensional structure.