Supercritical fluids (SCFs) process can be considered as an emerging”clean“technology for the production of small-size particles (e.g. micron-size). Microsphere is a material in micron scale which has been widely used as adsorbent, catalyst support, and drug delivery system. For advanced application, those materials are formulated in the form of porous microspheres. There are several methods that can be used using SCFs. One of them is Solution Enhanced Dispersion by Supercritical Fluids (SEDS). This method is considered to be suitable in obtaining the porous microsphere polystyrene. In this study, polystyrene was first dissolved into toluene (polystyrene solution) at different concentrations (i.e. 3, 5, 7, 9, 11, 13, 15 wt%) and then blown/sprayed together with supercritical carbon dioxide (CO2) through co-axial nozzle with two differents annulus diameter (i.e. 3.6 mm and 4.6 mm). Co-axial nozzle consists of two concentric pipes, inner pipe and annulus. Inner pipe for polystyrene solution flow and annulus for supercritical carbon dioxide flow. The expansion of these two of fluid was done both in atmospheric condition and in pressurized precipitator (40 bar). The resulted microsphere was analyzed by using SEM (Scanning Electron Microscope) to determine morphology and average diameter of the microsphere. The SEM analysis results showe that the smaller the initial concentration of solution used, the resulted microspheres tend to be smaller and less fibrils formed. Additionally, in the pressurized precipitator, the formed microspheres size was smaller and size distribution more narrow than that of atmospheric condition. Moreover, the use of smaller annulus diameter in co-axial nozzle produced smaller microsphere size and the size distribution was more uniform.