A novel liquid crystalline N-substituted pyrrole having an ionic viologen side chain was synthesized, and was polymerized by a FeCl3 method. Thermotropic liquid crystalline behavior of the pyrrole and the polymerized material were investigated by DSC, thermo-controlled polarizing optical microscopy, and XRD. The pyrrole derivatives showed two smectic phases between isotropic and crystalline (solid) phases. Viologen functions of redox and cation-radical generation for the pyrrole derivatives were confirmed by cyclic voltammetry with UV-Vis spectroscopy.