Thiacalixarenes are new members in the calixarene family, which are readily accessible by reacting p-alkylphenols with elemental sulfur using NaOH as a base catalyst. With the progress of work, it has been demonstrated that these sulfur-bridged macrocycles are not the simple substitute for parent calixarenes but have their own inherent properties due to sulfur functionality. This review discloses the syntheses and modifications of thiacalixarenes and development of their intrinsic functions that cannot be attained by the conventional methylene-bridged counterparts.