Abstract: A series of main-chain liquid-crystalline ionomers (MLCIs) were prepared by solution polycondensation reactions using sebacyl chloride (SD), 6, 6′-hydroxy-hexa-O-acety1-α, β-maltose (MA), 4, 4′-biphenyldid (MB) and 2, 5-dihydroxybenzoic (MC) as monomers. The mesomorphic properties of MLCIs were investigated by FT-IR, DSC and POM. Results show that MLCIs are thermotropic cholesteric liquid crystal polymers. Glass transition temperature, melting temperature and clearing point temperature increase with the increase of MC content. But the mesophase was destroyed with the increase of MC content. The introduction of ion does not change the type of mesophase.