A novel 3-D lead-iodide polymer [Pb2I(μ-bpt-z)3]n (1, Hbpt-z = 3,5-bis(pyrazinyl)-1,2,4-trizole) has been hydrothermally prepared and structurally characterized. 1 offers the first example of a 3-D lead-iodide polymer built up from the linkage of rare binuclear [Pb2I]3+ cations and anionic bis(pyrazinyl)-trizole bridges. 1 exhibits photoluminescent and photocurrent response properties, and its density functional theory calculation was also studied.