A new inorganic-organic hybrid solid, (4,4'-bipy)[Zn(HPO3)](2) (4,4'-bipy = 4,4'-bipyridine), has been hydrothermally synthesized in the presence of 4,4'-bipy ligand. Its structure was determined by single-crystal X-ray diffraction and further characterized by FTIR, elemental analysis, ICP analysis, powder X-ray diffraction, thermogravimetric analysis and fluorescent spectrum. It crystallized in the monoclinic space group, P2(1)/c, with a = 9.741(2), b = 7.4423(16), c = 10.271(2) Angstrom, beta = 100.038(4)degrees, V = 733.3(3) Angstrom(3), Z = 2. The structure consists of neutral sheets of zinc phosphite which is pillared through 4,4'-bipy ligands to generate a 3D framework. The compound shows relatively high thermal stability and exhibits intense photoluminescence upon photo-excitation at 362 nm. (C) 2003 Elsevier Inc. All rights reserved.