AB amphiphilic comb-like block copolymers of poly(oligo[ethylene glycol] methyl ether methacrylate) and polydimethylsiloxane were synthesised with a methodology based on atom transfer radical polymerization (ATRP). The anionic ring opening polymerisation of hexamethylcyclotrisiloxane followed by reaction with 3-(chlorodimethylsilyl) propyl 2-bromo-2-methylpropanoate propyldimethylchlorosilane gave suitable macroinitiators for the ATRP of oligo[ethylene glycol] methyl ether methacrylate. The latter synthetic procedure was optimised by performing a number of syntheses varying the reaction solvent, catalytic complex and the temperature used. Copolymers with relatively high polydispersity indices (M-w/M-n > 1.3) could be synthesised at room temperature by employing a Cu(I)Br:N,N,N',N,N"-pentamethyldiethylenetriamine complex in n-propanol with Cu(II)Br. The optimum reaction conditions employed a Cu(I)Cl:N-(n-propyl)-2-pyridyl(methanimine) complex with an n-propanol/water mixture or toluene as solvent at 90 degreesC. This gave block copolymers of the desired molecular weights and polydispersity indices of less than 1.1. The block copolymers were characterised with H-1 NMR and C-13 NMR spectroscopy and size exclusion chromatography. (C) 2004 Elsevier Ltd. All rights reserved.