Using 4-aminopyridine as the structure-directing agent(SDA), a new open-framework zinc phosphite, (C 5 H 7 N 2 ) 2 ·[Zn 3 (HPO 3 ) 4 ](ZnHPO-CJ70), was synthesized under hydrothermal condition. Single-crystal X-ray diffraction analysis reveals that ZnHPO-CJ70 is constructed by the strictly alternating ZnO 4 tetrahedra and HPO 3 pseudo-pyramids, with their vertexes linked to generate a three-dimensional(3D) open framework with intersecting 8- and 12-ring channels. Further characterizations of ZnHPO-CJ70 were performed by means of X-ray powder diffraction(XRD), elemental analysis(ICP, CHN), infrared spectroscopy(IR) and thermogravimetric(TG) analyses. The results of luminescent test shows that ZnHPO-CJ70 exhibits strong fluorescence emissions in the solid state at room temperature.