The　hybridization　of　1,4-bis(isoquinoline)butane　(BIQBT2+)　cation　with　iodobismuthate　under　different　solvents　produce　two　isomers　α-[(BIQBT)(BiI4)2]n　(α-1,　in　CH3OH/H2O　mixed　solvent,　Triclinic　system　with　P-1　space　group)　and　β-[(BIQBT)(BiI4)2]n　(β-1,　in　CH3OH,　Monoclinic　system　with　P21/c　space　group).　The　1-D　(BiI4)nn−　chains　are　constructed　from　the　opposite　edge-sharing　BiI6　octahedra.　The　(BIQBT)2+　in　α-isomer　adopts　the　planar　configuration,　and　that　in　β-isomer　presents　the　chair-like　configuration,　as　a　result,　different　packing　modes　(intercalating　quasi-3-D　mode　for　α-1　and　interlocking　2-D　mode　for　β-1)　are　observed.　Interestingly,　from　α-1　to　β-1,　distortion　degree　of　BiI6　octahedron　and　π–π　stacking　interaction　decrease,　but　hydrogen　bonds　number　increase.　Consequently,　due　to　different　packing　mode,　photoluminescence/thermochromisms　can　be　found　in　α-1,　but　those　of　β-1　are　vanished,　Theoretical　calculation　was　conducted　to　disclose　the　structure/thermochromism　correlation.　©　2020,　Springer　Science+Business　Media,　LLC,　part　of　Springer　Nature.