In this paper, polystyrene nanoparticles and polystyrene membrane were successfully synthesized. Polystyrene nanoparticles and their crosslinking were carried out, at 80 ⁰C temperature by soap-free emulsion polymerization. Polystyrene membrane was synthesized from Polystyrene nanoparticles and its crosslinking were treated with two organic solvents. The product of polystyrene nanoparticles from 399.2 to 621.1nm and Polystyrene nanoparticles shows the best results. The polystyrene membrane shows enhancement product treated with toluene and Tetrahydrofuran. The characterization of Polystyrene nanoparticles and their crosslinking and Membrane fabrications were done by SEM, and TEM.