Currently, numerous articles have reported pyridine-based thermotropic mesogens; however, reviews of their synthetic methodologies are rare. Therefore, the present critical review describes the recent synthetic advances in the field of pyridine-based thermotropic mesogens. Also, we discuss the various types of thermotropic mesogens (such as calamitic, discotic, bent-shaped, polycatenar, and polymeric mesogens) consisting of pyridine derivatives and their structure–property relationships.