The　hybridization　of　1,4-bis(isoquinoline)butane　(BIQBT(2+))　cation　with　iodobismuthate　under　different　solvents　produce　two　isomers　alpha-[(BIQBT)(BiI4)(2)](n)(alpha-1,　in　CH3OH/H2O　mixed　solvent,　Triclinic　system　withP-1　space　group)　and　beta-[(BIQBT)(BiI4)(2)](n)(beta-1,　in　CH3OH,　Monoclinic　system　withP2(1)/c　space　group).　The　1-D　(BiI4)nn-chains　are　constructed　from　the　opposite　edge-sharing　BiI(6)octahedra.　The　(BIQBT)(2+)in　alpha-isomer　adopts　the　planar　configuration,　and　that　in　beta-isomer　presents　the　chair-like　configuration,　as　a　result,　different　packing　modes　(intercalating　quasi-3-D　mode　for　alpha-1and　interlocking　2-D　mode　for　beta-1)　are　observed.　Interestingly,　from　alpha-1to　beta-1,　distortion　degree　of　BiI(6)octahedron　and　pi-pi　stacking　interaction　decrease,　but　hydrogen　bonds　number　increase.　Consequently,　due　to　different　packing　mode,　photoluminescence/thermochromisms　can　be　found　in　alpha-1,　but　those　of　beta-1are　vanished,　Theoretical　calculation　was　conducted　to　disclose　the　structure/thermochromism　correlation.