pH-responsive amphiphilic H-shaped copolymer was prepared by the supramolecular self-assembly between beta-cyclodextrin-graft-poly(2-(N,N-diethylamino)ethyl methacrylate) (beta-CD-(PDEAEMA)(2)) and bi-adamantyl terminated poly(epsilon-caprolactone) (Ad-PCL-Ad). beta-CD-(PDEAEMA)(2) was synthesized by click reaction of alkynyl-modified beta-CD with azide PDEAEMA (PDEAEMA-N-3). Ad-PCL-Ad was synthesized by the DCC reaction of bi-hydroxyl terminated PCL (HO-PCL-OH) with adamantaneacetic acid. The supramolecular copolymer can self-assemble into micelles in water at room temperature. The micellization and pH-responsivity of the amphiphilic copolymer solution were investigated by transmittance, dynamic light scattering spectrophotometer, and transmission electron microscopy in water. Investigation shows that the micelles' sizes can be adjusted through the alteration of the pH values of solutions and the supramolecular copolymer will have the potential applications in biomedical field.