A five-arm star-shaped poly(ethylene oxide) (PEO) with terminal bromide groups was used as a macroinitiator for the atom transfer radical polymerization of tert-butyl acrylate (tBA), resulting in five-arm star-shaped poly(ethylene oxide)-blockpoly(tert-butyl acrylate) block copolymers. The polymerization proceeded in a controlled way using a copper(I)bromide/pentamethyl diethylenetriamine catalytic system in acetonitrile as solvent. The hydrolysis of the tBA blocks of the amphiphilic star-shaped PEO-b-PtBA block copolymer resulted in dihydrophilic star structures. The encapsulation of the star-block copolymers and their release properties in acid environment have been followed by UV-spectroscopy and color changes, using the dye methyl orange as a hydrophilic guest molecule. Characterization of the structures has been done by H-1 NMR, size exclusion chromatography, MALDI-TOF, and differential scanning calorimetry. (C) 2007 Wiley Periodicals, Inc.