Two novel Zn2+ organic phosphonate Zn(4,4′-bipy)(HBCP) 1 and ［Zn2(phen)2(BCP)(H2BCP)］·H2O 2 were hydrothermally synthesized. The compound 1 is with two-dimensional layer framework whereas the compound 2 is zero- dimensional structure. The Zn2＋ion is four-coordinated in compound 1 while five or six-coordinated in compound 2. The relationship between their properties and structures was studied by using FTIR, two-dimensional (2D) correlation infrared spectroscopy under thermal perturbation, fluorescence and UV-Vis DRS spectrum etc. Upon light excitation at 350 nm, the compound 1 exhibits luminescence with a strong wide emission at 412 nm and a weak emission at 520 nm, while the compound 2 exhibits luminescence with a wide emission only at 398 nm under light excitation at 336 nm.