Replacement of linear ligand L in Cu'XL system (X = halide or pseudohalide; L = 4,4'-bipyridine or pyrazine) by neutral species Cu(pzc)(2)(H2O)(x) (pzc = 2-pyrazinecarboxylate) resulted in mixed-valence Cu(I,II) coordination polymers [Cu-2(pzc)(2)Br(H2O)] (1) and [Cu-3(pzc)(2)(CN)(2)(H2O)(2)(.)2H(2)O](n) (2). Complex 1 has two-dimensional (4,4) topological layer constructed by [CuBr](n) chains and Cu(pzc)(2)(H2O) species, while 2 has a three-dimensional framework formed by linkage of two-dimensional (6,3) layers via ligand-unsupported Cu(I)-Cu(I) interactions. The two-dimensional (6,3) layer in 2 is constructed by zigzag [CuCN](n) chains and Cu(pzc)(2)(H2O)(2) species. Cyanides in 2 were produced by oxidative desulfation of SCN- anions.