The synthetic strategies towards tetraphenylene derivatives are comprehensively summarized in this review. Recent advances in the functionalized tetraphenylene skeleton for research into their structurally unique properties are described together with their potential applications.

Developments of tetraphenylene chemistry in our laboratories (Shanghai and Hong Kong) since 2009 are summarized. The properties and new applications of the structurally unique tetraphenylene derivatives are described in the context of helical macrocycles, asymmetric catalysis, host–guest chemistry, and liquid crystalline molecules. Some future challenges in this field are also presented. 1 Introduction 2 Structure and Properties of Tetraphenylenes 3 Tetraphenylenes and Helical Macrocycles 4 Tetraphenylenes and Asymmetric Catalysis 5 Tetraphenylenes and Host–Guest Chemistry 6 Tetraphenylenes and Liquid Crystalline Molecules 7 Conclusion and Perspectives