A series of core/shell particles were prepared by sequential emulsion polymerization. The core/shell particles consisting of poly(methyl methacrylate) core grafted with using rubbery layer [poly(butyl acrylate)co-(styrene)] and then glassy layer [poly(methyl methacrylate)-co-(ethyl acrylate)] were prepared. The conditions which led to controlled particle size and morphology were discussed. A highly cross-linked structure was formed in both the cores and the shells by using a cross-linking agent, which could prevent the migration of hydrophobic shells to the inside of the particles. The core/shell particles were characterized by Fourier-transform infrared spectroscopy, solid state C-13-NMR. Thermogravimetric analysis (TGA) and differential scanning calorimeter (DSC) were used to determine the thermal stability and glass transition temperature of the core/shell particles, respectively. Results of the particle size analysis indicate that particle sizes were decreased when there is a rubbery layer as outer layer (0.44 mu m) whereas it increases when there is a glassy layer as outer layer (324 mu m). Scanning electron microscopy (SEM) also confirms the multi-layers formation in the polymer. (C) Koninklijke Brill NV, Leiden, 2010