Particles of sizes within the nano region have attracted many applications in different fields of science. In this study, the self assembly property in a selective solvent of block copolymers has been used for the preparation of polystyrene nanospheres. Sulfonated Styrene-Butadiene-Styrene (SSBS) tri block copolymer was used as a polymeric surfactant for synthesis of uniformly sized polystyrene nanoparticles using emulsion polymerization. The effects of initiator, monomer and block copolymer concentration to the molecular weight distribution and size distribution were investigated. Uniformly sized nanoparticles with a polydispersity index of 1.004 and diameter of 112.9nm was verified by Dynamic Light Scattering (DLS) and Scanning Electron Microscopy (SEM), respectively. Using a mixed continuous phase solution of water and methanol, it was found out that the particle size decreased relative to the increase of methanol added to the reaction solution. Associating behavior of the polyelectrolyte block copolymer in the binary solvent environment regarding size of micelle formed was reflected on the properties of the nanospheres. Nanoparticles prepared with greater methanol concentration were observed to be less than 100 nm. Size distribution was also observed to be narrower in proportion to MeOH concentration.