Four one-dimensional complexes, denoted as [NiL1][Ni(CN)4] (1), [CuL1][Ni(CN)4] (2), [NiL2][Ni(CN)4]·2H2O (3), and [CuL2][Ni(CN)4]·2H2O (4) (L1= 1,8-dimethyl-1,3,6,8,10,13-hexaaza-cyclotetradecane; L2= 1,8-dipropyl-1,3,6,8,10,13-hexaazacyclotetradecane) were synthesized by reacting nickel/copper macrocyclic complexes with K2[Ni(CN)4]. Subsequently, the synthesized complexes were characterized using elemental analysis, infrared spectroscopy analysis, thermogravimetric analysis, and X-ray powder diffraction. Single-crystal structure analysis revealed that the Ni(II)/Cu(II) atoms were coordinated by two nitrogen atoms from [Ni(CN)4]2−with four nitrogen atoms from a macrocyclic ligand, forming a six-coordinated octahedral coordination geometry. Nickel/copper macrocyclic complexes were bridged by [Ni(CN)4]2−to construct one-dimensional chain structures in1–4. The characterization results showed that the four complexes obeyed the Curie–Weiss law with a weak antiferromagnetic exchange coupling.