A series of P[(HEMA-TMS)-co-PEOMA] graft copolymers with different amounts of incorporated macromonomer grafts were prepared by copolymerization of a PEO macromonomer (PEOMA, MWav = 1100 g/mol, DPPEO = 23) with 2-(trimethylsilyloxy)ethyl methacrylate (HEMA-TMS) using various initial ratios of the comonomers via atom transfer radical polymerization. After transformation of the HEMA-MS units to 2-(2-bromopropionyloxy)ethyl methacrylate (BPEM), the resulting P(BPEM-co-PEOMA) copolymers were used as macroinitiators for the controlled polymerization of n BA in a 'grafting from' reaction. The resulting densely heterografted brush copolymers with a uniform length of PEO grafts (DPPEO = 23) and a range of lengths for the Pn BA side chains (DPPn BA = 15-60) depending solely on the reaction time. Analysis of the bulk properties showed that the specific architecture of the copolymers suppresses crystallization of the PEO, and consequently leads to amorphous, homogeneous materials. (C) 2003 Elsevier Ltd. All rights reserved.