One-dimensional cyanide-bridged bimetallic coordination polymer [CuL(H 2O) 2] n [(CuL)·(μ-CN) 2Fe(CN) 4] 2n ·(H 2O) 2n was synthesized and structurally characterized. The coordination polymer crystallizes in a monoclinic system of the space group C2/c with a=2.983 1(5) nm, b=1.527 4(3) nm, c= 1.725 3(4) nm, β=107.68(2)°, V=7.490(3) nm3, Z=8, D c=1.382 g/cm3, F(000)=3 260, R=0.059 3, wR 2=0.132 3, S=0.885. The one-dimensional zigzag chain extents through Cu—CN—Fe—CN—Cu linkages. The adjacent two polymer chains are linked by the O—H……NC hydrogen bonding between [CuL(H 2O) 2] 2+ and [Fe(CN) 6] 3- ions to form hydrophilic channels in which water molecules are included.