The aim of this review is to summarize and highlight the rapidly expanding area of nitroxide radical coupling reactions, including atom transfer nitroxide radical and single electron transfer nitroxide radical coupling reactions, in polymer and material synthesis. Initial discussion is focused on the influencing factors, e.g. temperature, solvent, catalyst and the structure of reactant, on the reaction rate and efficiency. In addition, this review attempts to demonstrate the broad applications of nitroxide radical coupling reactions on the terminal functionalization of polymers, the synthesis of polymers with complex and well-defined architecture, and the preparation of organic–inorganic composites. Finally, the current challenges and future directions of nitroxide radical coupling reactions are also discussed.
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