A 1D zinc(II) coordination polymer with W-like pentanuclear secondary building blocks constructed by 2,6-bis[(3-methoxysalicylidene)hydrazinocarbonyl]pyridine (H 4 Bmshp) ligand, {[Zn 5 (Bmshp)(CH 3 COO) 5 Cl(H 2 O) 3 ]Á 2H 2 O} n , was synthesized and characterized by elemental analysis, IR, X-ray diffraction, and thermogravimetric analyses. It has the highest nuclear unit constructed by one 2,6-pyridine-diacylhydrazone ligand so far. The luminescent property of the compound was studied. It shows an emission with a maximum at 522 nm upon excitation at 450 nm.