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The design and synthesis of heterometallic iodoplumbates have attracted much interest due to the diverse structures and significant physical properties. A Pb/CuI/I heterometallic iodoplumbate, [PbCu2I4(bipy)]n (1) (bipy = 2,2′-bipyridine), has been synthesized by solvothermal reaction of PbI2, Cu(NO3)2, bipy, and HI, and characterized by single-crystal X-ray diffraction, powder X-ray diffraction, and thermogravimetric analysis. This compound exhibits one-dimensional neutral structure, which is built upon the linkages of Pb/I chains, Cu/I chains, and Cu(bipy) units. The yellow compound has an optical bandgap of 2.32 eV and shows fluorescent emission at 610 nm which is assigned to iodide-to-copper charge transfer.