Polymerizable vinylimidazolium ionic liquids (ILs) that contain mesogenic coumarin and biphenyl units, respectively, have been synthesized. The N‐alkylation of N‐vinylimidazole with bromoalkylated mesogenic units 7‐(6‐bromohexyloxy)coumarin ( 1 ) and 4,4′‐bis(6‐bromohexyloxy)biphenyl ( 2 ) was then carried out. The thermal behavior of the obtained ILs 3 and 4 was investigated by differential scanning calorimetry and polarizing optical microscopy. These measurements showed that the attached mesogenic units induce the self‐assembly of ILs and, therefore, the occurrence of liquid crystalline phases. Subsequently, the ionic liquid crystals (ILCs) 3 and 4 were polymerized by a free‐radical mechanism.
