The 3D acentric metal-organic framework (MOF) of [Zn(Mitz)Cl](n) [1; Mitz = 3-tetrazolyl-6-methyl-5-(4-pyridyl)-2-pyridone] was obtained from in situ [2 + 3] cycloaddition reactions of milrinone [=3-cyano-6-methyl-5-(4-pyridyl)-2-pyridone] with sodium azide in the presence of ZnCl2 as the Lewis acid. The compound is a typical ferroelectric material with an electric hysteresis loop showing a remnant polarization (P-r) of ca. 0.21 mu C/cm(2) and a coercive field (E-c) of 2600 V/cm. Powdered samples of 1 display strong second-harmonic-generation responses of similar to 2 times larger than that of KH2PO4. Photo luminescent study show that complex 1 and the milrinone ligand exhibit maximal emission peaks at around 409 and 401 nm, respectively, in the solid state at room temperature.