Two novel complexes of CuCN were characterized by using a single-crystal X-ray diffraction technique and Raman spectroscopy. In the structure of 2CuCN·DMSO ligand molecule demonstrates unique bridging mode, being bound to two CuI centers via oxygen and sulfur atoms. The bridging role of both CN groups and DMSO molecules results in the formation of (CuCN·DMSO)n framework. Along the channels of the network are running infinite zig-zag (CuCN)n chains, which are bound to the framework by elongated Cu…(CN) bonds. A mixed-valence [CuII(DMSO)6][CuI
6(CN)8] compound is composed of 3-D [CuI
6(CN)8]n anionic framework and located in the channels of partially disordered [CuII(DMSO)6]2+ cations.