Catalytic action of an enzyme is shown to transform a non-assembling block copolymer, composed of a completely non-natural repeat unit structure, into a self-assembling polymer building block. To achieve this, poly(styrene) is combined with an enzyme-sensitive methacrylate-based polymer segment carrying carefully designed azobenzene side chains. Once exposed to the enzyme azoreductase, in the presence of coenzyme NADPH, the azobenzene linkages undergo a bond scission reaction. This triggers a spontaneous 1,6-self-elimination cascade process and transforms the initially hydrophobic methacrylate polymer segment into a hydrophilic hydroxyethyl methacrylate structure. This change in chemical polarity of one of the polymer blocks confers an amphiphilic character to the diblock copolymer and permits it to self-assemble into a micellar nanostructure in water.