Five novel Zinc (II) metal-organic hybrid materials, [(ZnCl 2 L) 6 ·6(H 2 O)·6(CHCl 3 )] (1), [(ZnBr 2 L) 6 ·6(H 2 O)·6(CHCl 3 )] (2), [ZnI 2 L·2(CHCl 3 )] n (3), [Zn(SCN) 2 L·(CHCl 3 )] n (4), and [Zn(CHCOO) 2 L·2(H 2 O)] n (5), have been assembled by a novel ligand 4′-ferrocenyl-4, 2′: 6′, 4″-terpyridine and different zinc salts under ambient conditions, and their structures have been confirmed by single-crystal X-ray diffraction analysis. The results indicate that both complexes 1 and 2 adopt a metallohexacycle consisting of six ligands and six zinc ions, and complexes 3, 4 and 5 are all one-dimensional polymers. The supramolecular frameworks are constructed by complexes 1–5 through the C–H⋯X (X = Cl, Br, I, S, O or π) or π–π intermolecular interactions. In addition, the optical band gaps were confirmed by use of the optical diffuse reflectance spectra, and the results show that the ligand and complexes 1–5 should have semiconductor properties.