AbstractWell‐defined functional star‐shaped polymer structures with up to 29 arms have been successfully synthesized by the combination of atom transfer radical polymerization (ATRP) and click chemistry. First, azide end‐functionalized poly(isobornyl acrylate) (PiBA) star‐shaped polymers were prepared by successive ATRP and bromine substitution. Subsequently, alkyne end‐functionalized molecules and polymers were introduced onto the star‐shaped PiBA bearing pendant azide moieties by copper‐catalyzed azide–alkyne cycloaddition (CuAAC). The possibilities and limits for the CuAAC on such highly branched polyacrylates are described.magnified image