Two novel hybrid Bi(III) supramolecular compounds based on guest cations and 18-crown-6, [(1,4-PMNH3)·(18-crown-6)]3·0.5(1,4-PMNH2)·0.5(18-crown-6)·(Bi2Cl9)] (1) and [(OH3)·(18-crown-6)]2·2(H3O)·2(H2O)·(Bi2Cl10)] (2), have been synthesized through controlling the reaction conditions, respectively, and characterized by single crystal X-ray diffraction, elemental analysis, IR, XRPD, UV, DSC, TGA, proton NMR and luminescence (1,4-PMNH2=1,4-phenylenedimethanamine). The rotator–stator assemblies, [(1,4-PMNH3)·(18-crown-6)]+ and [(OH3)·(18-crown-6)]+, were formed by the guest cations inserting into crown ether macrocycle through strong N(O)H⋯O H-bonding interactions. These ions and molecules were alternately stacked together to build the two different supramolecular compounds.