Multifunctional initiators for atom transfer radical polymerization (ATRP) are prepared by converting ditrimethylolpropane with four hydroxyl groups, dipentaerythritol with six hydroxyl groups, and poly(3-ethyl-3-hydroxymethyl-oxetane) with similar to 11 hydroxyl groups to the corresponding 2-bromoisobutyrates or 2-bromopropionates as obtained by reaction with acid bromides. Star polystyrene (PS) is produced by using these macroinitiators and neat styrene in a controlled manner by ATRP at 110 degrees C, employing the catalytic system CuBr and bipyridine. M. up to 51,000 associated with narrow molecular weight distributions (PDI < 1.1) are obtained with conversions up to 32%. Hydrolysis of the star-PS leads to linear chains having the expected M-n values. The star-PS polymers based on dipentaerythritol degrade thermally in nitrogen in a two-step process in which the first low-temperature step involves scission of the ester linkages and the second step corresponds to the normal PS degradation. Star poly(methyl acrylates) with various cores are likewise prepared in a controlled manner by ATRP of methyl acrylate in bulk and in solution at 6080 degrees C with the 1,1,4,7,7-pentamethyldiethylene triamine ligand. Under these conditions, higher conversions were possible still maintaining low PDI signaling controlled star growth. Multiarm stars of poly(n-butyl acrylate) and poly(n-hexyl acrylate) with controlled characteristics have also been prepared. (c) 2005 Wiley Periodicals, Inc.