Nitroxide-mediated crosslinking radical copolymerizations of styrene and divinylbenzene have been carried out in aqueous mimemulsion with Dowfax 8390 as surfactant at 125 degrees C employing TEMPO-based macroinitiators of various hydrophilicities (random copolymers comprising styrene and methyl acrylate). The pendant conversion (i.e. the degree of crosslinking) increased with increasing macroinitiator hydrophilicity and with decreasing particle size. It is proposed that a concentration gradient is generated within the particle such that the macroinitiator concentration tends to be higher near the oil-water interface than in the particle interior. The macroinitiators are surface active and are thus preferentially adsorbed at/located near the oil-water interface. This in turn leads to an increase in the ratio [pendant unsaturation]/[monomer] in the vicinity of propagating radicals, which are generated from the macroinitiators, and thus an increase in pendant conversion. This effect is enhanced by an increase in macroinitiator hydrophilicity and a decrease in particle size. The present approach offers novel means of controlling network formation in dispersed systems. (C) 2009 Elsevier Ltd. All rights reserved.