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Hetero-dendronized copolymers can be obtained in a single step using “orthogonal” click reactions, as reported by Murat Tonga, Gulen Yesilbag Tonga, Gonca Seber, Ozgul Gok, and Amitav Sanyal on page 5029. Huisgen-type alkyne–azide and the Diels–Alder cycloaddition reactions are utilized to decorate a polystyrene copolymer containing pendant azide and anthracene functional groups by reacting with polyaryl and polyester dendrons appended with an alkyne and a masked maleimide group at their focal points. The methodology highlights the utility of the click reactions to enable construction of complex polymeric structures in a simple and convergent manner.