This report describes the synthesis and structural characterizations of three new complexes; [Na₃Fe₂(bbp)(Hbbp)(CN)₆(H₂O)₉]4H₂O (1), (Bu₄N)[Fe(bbp)₂].3CH₃OH.2H₂O (2), and a cyano-bridged dinuclear copper(II) complex, [Cu₂(tren)₂(CN)][Fe(bbp)₂]₃ 6CH₃OH.4H₂O (3), where H₂bbp = bis(2-benzimidazolyl) pyridine and tren = tris(2-aminoethyl)amine. X-ray crystallography reveals that the geometry of iron(III) centers in the complex anions of 1–3 is an octahedral, while it is a trigonal bipyramidal around copper(II) center in the complex cation of 3. Both bbp ligands meridionally coordinate iron(III) centers in the complex cations of 2 and 3, while three cyanide ions and bbp (or Hbbp) ligand occupied either of the meridional positions around the metal center in 1. In the dinuclear complex cation of 3, the Cu(II)-CN-Cu(II) bridging region is strictly linear as dictated by the symmetry with Cu...Cu separation of 5.084 (7) A^° . Variable temperature magnetic susceptibility study shows that the cyano-bridge mediates the antiferromagnetic coupling between copper(II) centers with J value of -110 K in 3.