Copper-based atom-transfer radical polymerization for a template monomer with 10.9 methacryloyl groups, which was synthesized with beta-cyclodextrin by the esterification of secondary hydroxyl groups with methacrylic acid anhydride, was carried out with 1,3-dibromobutane, 1,1,4,7,10,10-hexamethyltriethylenetetramine, and CuBr as an initiator, a ligand, and a catalyst, respectively. The effects of solvent, polymerization temperature, and molar ratio of the initiator to the template monomer on polymerization were investigated. The progress of polymerization was investigated by kinetic analysis of conversion and the molecular weight of methacrylic acid oligomers (PMAA) obtained by hydrolysis of the polymerized products by get permeation chromatrography and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Increasing the polymerization temperature and tetrahydrofuran caused an increase of the polydispersity of PMAA.