This article reviews the design of polymeric functional spaces with microgel-core star polymers and single-chain folding/crosslinked polymers via living radical polymerization for unique functions. Core-functionalized star polymers were prepared by the intermolecular linking of arm polymers with functional linkers/monomers to provide solubilized microgel spaces for active and recyclable catalysis and selective and stimuli-responsive molecular recognition. Single-chain folding and crosslinked polymers were in turn obtained from the self-folding and/or intramolecular linking of amphiphilic random copolymers carrying hydrophilic poly(ethylene glycol) chains and hydrophobic alkyl pendants in water.
