Pillar[ n ]arenes are a novel class of macrocyclic hosts reported by Ogoshi and co-workers in 2008. Because of their rigid pillar structures, interesting host-guest properties and ease of modifications, pillar[ n ]arenes have been developed rapidly in the field of functional materials and biomedicine. The modifications of pillar[ n ]arenes at different positions can give them varied characteristics. Functional groups can be introduced into one position of pillar[ n ]arenes without changing host- guest properties of pillar[ n ]arenes. A series of pillar[ n ]arene dimers, trimers, tetramers and metallacycles can be constructed by mono-functionalized pillar[ n ]arenes. In this review, two synthetic methods of mono-functionalized pillar[ n ]arenes are summarized and structures containing monofunctionalized pillar[ n ]arenes are described. Furthermore, the applications of mono-functionalized pillar[ n ]arenes in different fields ( e.g. , supramolecular polymers, sensors, molecular machines, catalysis, biological applications and light-harvesting systems) are also introduced. Hopefully, this article will be useful for researchers studying pillar[ n ]arenes, especially the mono-functionalized pillar[ n ]arenes.(c) 2023 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.