A one-pot free radical polymerization process was used to prepare methyl acrylate/ethylene glycol dimethacrylate (MA/EGDMA) and methyl methacrylate/ethylene glycol dimethacrylate (MMA/EGDMA) polymers. The role of monomer and crosslinker reactivity ratios in producing different network structures was demonstrated. While both systems produced branched polymers that exhibited low intrinsic viscosities with little variation across a wide range of molecular weights, the star-like microgels formed between a less reactive monomer (MA) with a more reactive crosslinker (EGDMA) gave lower bulk solution viscosities than the more statistical polymers formed between similarly reactive monomers and crosslinkers (MMA and EGDMA). This paper presented a simple and cost-effective synthetic route for the production of polymers with high molecular weight and low viscosity with considerable potential for industrial-scale processing. (c) 2005 Elsevier Ltd. All rights reserved.