Bismuth-halide-based　inorganic-organic　hybrid　materials　(Bi-IOHMs)　are　desirable　in　luminescence-related　applications　due　to　their　advantages　such　as　low　toxicity　and　chemical　stability.　Herein,　two　Bi-IOHMs　of　[Bpy][BiCl4(Phen)]　(1,　Bpy　=　N-butylpyridinium,　Phen　=　1,10-phenanthroline)　and　[PP14][BiCl4(Phen)]center　dot　0.25H(2)O　(2,　PP14　=　N-butyl-N-methylpiperidinium),　containing　different　ionic　liquid　cations　and　same　anionic　units,　have　been　synthesized　and　characterized.　Single-crystal　X-ray　diffraction　reveals　that　compounds　1　and　2　crystallize　in　the　monoclinic　space　group　of　P2(1)/c　and　P2(1),　respectively.　They　both　possess　zero-dimensional　ionic　structures　and　exhibit　phosphorescence　at　room　temperature　upon　excitation　of　UV　light　(375　nm　for　1,　390　nm　for　2),　with　microsecond　lifetime　(24.13　mu　s　for　1　and　95.37　mu　s　for　2).　Hirshfeld　surface　analysis　has　been　utilized　to　visually　exhibit　the　different　packing　motifs　and　intermolecular　interactions　in　1　and　2.　The　variation　in　ionic　liquids　makes　compound　2　have　a　more　rigid　supramolecular　structure　than　1,　resulting　in　a　significant　enhancement　in　photoluminescence　quantum　yield　(PLQY),　that　is,　0.68%　for　1　and　33.24%　for　2.　In　addition,　the　ratio　of　the　emission　intensities　for　compounds　1　and　2　shows　a　correlation　with　temperature.　This　work　provides　new　insight　into　luminescence　enhancement　and　temperature　sensing　applications　involving　Bi-IOHMs.