A novel route towards the synthesis of well‐defined linear–dendronized diblock copolymers is reported. Precursor alkyne containing diblock copolymers were modified in a highly efficient cycloaddition reaction with dendritic azides of different generation. The dendronization has been shown to be selective and could be driven to completion under ambient conditions. The phase separation of such dendronized diblock copolymers was investigated in dependence of the generation size being attached. Compared to a linear–linear diblock copolymer as starting material the dendronization yielded in a pronounced phase separation. The nanoscaled features observed in thin films strongly depended on the dendron size and a variety of morphologies could be identified. Hence, the unique combination of controlled radical polymerization and click chemistry allows for the triggering of structured surfaces in the nanometer‐regime.
