A novel type of pH-responsive star polymer based on beta-cyclodextrin (beta-CD) was synthesized and further covalently conjugated with enzyme. The impact of its self-assembly behavior on enzyme activity was investigated. In our design, azide containing the polymer (N-3)(7)-beta-CD-(PtBA)(14) was synthesized via atom transfer radical polymerization of tert-butyl acrylate using (N-3)(7)-beta CD-(Br)(14) as the multifunctional initiator. The final product (N-3)(7)-beta-CD-(PAA)(14) was obtained via hydrolysis and covalently conjugating pectinase onto pH-responsive polyacrylic acid (PAA) arms. PAA can change its conformation with the self-assembly by altered pH, leading its nanostructure into micellar nanoparticles in aqueous solution and further affecting the activity of immobilized pectinase. The results were proved by fluorescence spectroscopy and dynamic light scattering. This system proves that the activity of immobilized enzyme can be tailored predictably, and this pH-responsive polymer holds great potential for controllable delivery of enzymes. (C) 2016 International Union of Biochemistry and Molecular Biology, Inc.