A new approach to micellar polymerization is described. It is well known that hydrocarbons and fluorocarbons exhibit local phase segregation (demixing) owing to mutual antipathy; here this effect is employed in monomer swollen micelles with appropriate combinations of hydrocarbon and fluorocarbon monomers and surfactants. A matrix of these hydro- and fluorocarbon components has been investigated to delineate the effects of H-F antipathy on the outcomes of polymerization reactions to generate nanolatices of different size (and possibly morphology). Phase diagrams, H-1 NMR and small-angle neutron (SANS) data have been generated to characterize the systems, indicating new routes to influence nanolatex formation. (C) 2008 Elsevier Inc. All rights reserved.