A novel 3D Pb-II-organic framework {Pb(AIA)(2)}(n) (denoted as 1) can be successfully constructed by the assembly of 5-aminonicotinic acid (HAIR) and Pb-II cation under hydrothermal condition. The prepared 1 can be investigated and characterized by many technologies, including single-crystal X-ray diffraction, powder X-ray diffraction, luminescent spectrum, elemental analysis (C, H, and N), UV-Vis spectrum, as well as thermogravimetric analysis, respectively. The resultant 1 has lots of uncoordinated pyridine nitrogen atoms and -NH2 in the structure, which can be commonly considered as Lewis basic sites to catalysis Knoevenagel condensation reaction. Meanwhile, the as-synthesized 1 with the luminescent property can be considered as a luminescent sensor for selective sensing of Cr2O72- with excellent recyclability at least reusing four runs.