A novel 1-D iodoplumbate hybrid, 2（Pb3I9）^3＊·3（C14H18N2）^2＋ 1, has been hydrothermally synthesized and characterized by IR spectra, TGA and single-crystal X-ray diffraction. Complex 1 crystallizes in monoclinic, space group P21/c, with a = 12.057（2）, b = 14.024（3）, c = 24.742（5） A, β = 90.48（3）°, V = 4183.6（14） A^3, Z = 4, R= 0.0477 and wR = 0.0800. The title compound consists of 1-D chains （Pb3I9）n^3n＊ parallel to the [100] direction and stacks of alkylated 4,4＇-bipyridium cations running along the [011] direction. Each anionic chain is surrounded by six arrays of alkylated 4,4＇-bipyridium cations through extensive C-H…I atypical hydrogen-bonding interactions to afford an interesting 3-D supramolecular network. Significant fluorescent property of the compound was observed at room temperature.
