The polymerization of vinyl monomers with cleavable enzymatic substrates has been shown to lead to water-soluble double-hydrophilic block copolymers which, upon enzymatic activation of the diblock copolymers, become amphiphilic and undergo Self-assembly into colloidal nanostructures. The ability to change the chemical and physical characteristics of polymeric materials by an enzymatic reaction opens the way for novel and exciting applications such as enzymatic-triggered activation of surfaces and formation of nanostructures in vivo in a highly controlled manner.