Gelation in 2,2,6,6-tetramethylpiperidinyi-1-oxy (TEMPO)-mediated cross-linking copolymerization of styrene and divinylbenzene (8.2 rnot%) in aqueous miniemulsion at 125 degrees C has been investigated. The rate of gel formation relative to monomer conversion was the same in miniemulsion and the corresponding solution polymerization when the organic phase contained 6 vol% tetradecane (TD; hydrophobe) and 48 vol% toluene. However, at 54 vol% TD and no toluene (the same total monomer concentration), the conversion at the gel point was lower in miniemulsion than in solution, consistent with our previous results describing enhanced apparent pendant reactivity related to the presence of TD in the present system. The primary chain lengths were higher in miniernulsion with 54 vol% TD than in miniemulsion with 6 vol% TD and in solution (6 and 54 vol% TD). It was deduced via application of Flory-Stockmayer gelation theory that this difference in primary chain lengths, although significant with regards to gelation, was insufficient to explain the rapid gel formation in the miniemulsion containing 54 vol% TD, which is speculated to be related to specific effects of the heterogeneity of the miniemulsion system. (c) 2007 Elsevier Ltd. All rights reserved.