Abstract The application of photochemistry in polymer synthesis is of interest due to the unique possibilities offered compared to thermochemistry, including topological and temporal control, rapid polymerization, sustainable low‐energy processes, and environmentally benign features leading to established and emerging applications in adhesives, coatings, adaptive manufacturing, etc. In particular, the utilization of photochemistry in controlled/living polymerizations often offers the capability for precise control over the macromolecular structure and chain length in addition to the associated advantages of photochemistry. Herein, the latest developments in photocontrolled living radical and cationic polymerizations and their combinations for application in polymer syntheses are discussed. This Review summarizes and highlights recent studies in the emerging area of photoinduced controlled/living polymerizations. A discussion of mechanistic details highlights differences as well as parallels between different systems for different polymerization methods and monomer applicability.
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