A　new　heterometallic　iodide,　PbI4Cu2(PPh3)(4),　was　synthesized　by　reactions　of　PbI2,　CuI　and　triphenylphosphine　(PPh3)　in　DMF　solution.　The　single-crystal　X-ray　diffraction　analyses　show　that　Pb(II)　center　adopts　an　unusual　cis-divacant　octahedral　geometry.　Crystal　data:　triclinic,　space　group　P　(1)　over　bar,　a　=　12.3455(2)angstrom,　b　=　13.8673(1)angstrom,　c　=　21.3421(1)angstrom,　alpha　=　106.623(4)degrees,　beta　=　103.478(6)degrees,　gamma　=　93.574(5)degrees,　V　=　3371.83(6)angstrom(3)　and　Z　=　2.　Density　function　theory　(DFT)　calculations　and　fragment　orbital　interaction　analyses　reveal　the　presence　of　a　three-center　four-electron　(3c-4e)　hypervalent　bonding　about　lead;　and　the　formation　of　the　unusual　cis-divacant　[PbI4](2-)　octahedron　is　energetically　favorable.　The　title　yellow　compound　has　an　optical　bandgap　of　2.69　eV　and　shows　remarkable　red-infrared　fluorescence　emission　at　732　nm　with　lifetime　of　24　mu　s　which　is　assigned　as　an　iodine　5p-lead　6s　to　PPh3-lead　6p　charge　transfer　(XM-LM-CT).　(c)　2006　Elsevier　Inc.　All　rights　reserved.