Thermotropic ionic liquid crystals with a pyridinium skeleton were synthesized and the effects of counter ions for the liquid crystal formation were examined. The liquid crystal formation depended on the counter anions. The pyridinium liquid crystal, having chloride counter ion, showed columnar, cubic, and smectic A phases. The pyridinium liquid crystals with polymeric counter ions formed columnar and cubic phases. However, they did not show a smectic A phase. The polymeric counter ions enhanced the thermal stability of the cubic phase when compared to chloride counter ion.