Using　1,1΄-bis(isoquinoline)-1,4-phenyldimethylenyl　(BIQPM2+)　cation　as　template,　a　new　tetrameric　(Bi4I16)4-　iodobismuthate-containing　hybrid　with　formula　of　(BIQPM)2(Bi4I16)·H2O　(1),　has　been　prepared　under　solvothermal　conditions.　The　centrosymmetric　Bi4I16　4-　tetraanion　is　constructed　from　four　edge-shared　slightly　distorted　BiI6　octahedrons.　Due　to　the　presence　of　larger　conjugated　system　(isoquinoline　ring),　strong　π···π　stacking　interactions　can　be　observed.　Besides,　strong　I···I　interactions　can　be　monitored　and　extends　the　0-D　Bi4I16　4-　cluster　to　a　quasi-1-D　chain.　The　smaller　energy　gap　of　2.13　eV　is　led　by　these　non-covalent　interactions.　Its　infrared　emission　might　be　caused　by　strong　charge　transfer　between　anions　and　cations.　Furthermore,　the　reversible　thermochromic　behavior　with　low　chromotropic　temperature　of　80　℃　can　be　observed,　whose　mechanism　was　discussed.　©　2019　Fujian　Institute　of　Research　of　the　Structure　of　Matter.　All　rights　reserved.