The emulsion polymerization of divinyl monomers is investigated. Emulsions were obtained in the presence of sodium dodecyl sulfate and bis(2-ethylhexyl)sulfosuccinate sodium salt as surfactants. The influence of monomer type and kind of surfactant on the particle size distribution is studied. The porous structure of the broken emulsions is also determined. The results indicate that the diameter of nanospheres obtained from two divinyl monomers are significantly larger than those obtained from polystyrene. Aggregation of the particles and the pore-forming diluent added to the emulsion are responsible for the existence of pores.