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In this video abstract for http://MaterialsViews.com , the group of Barner-Kowollik (Karlsruhe Institute of Technology, Germany) report on using a photo-induced Diels-Alder reaction for the modular construction of a block copolymer at ambient temperature. Highly reactive dienes generated in-situ by UV-irradiation of 2-methylbenzophenone precursors react rapidly with maleimide functional poly(methyl methacrylate) prepared via atom transfer radical polymerization (ATRP). The concept is applied to the formation of a block copolymer utilizing 2,5-dimethylbenzophenone capped poly(ε-caprolactone) obtained from ring-opening polymerization (ROP). The new method provides a proof-of-principle that for the first time a means for the highly efficient conjugation of two polymeric building blocks triggered by light has been devised. This concept opens the door to variable applications, such as the locally constrained surface grafting of biomacromolecules, photo-induced polymer network formation and step-growth polymerization.