Abstract: Using monodispersed micron sized PS microspheres as template, EDOT as monomer and APS as initiator, the core shell PS-PEDOT conductive microspheres were synthesized by chemical oxidation polymerization. The morphology and structure of PS PEDOT were characterized by SEM and TEM. The characteristic of core shell structure of PS-PEDOT microspheres was emphatically studied by Raman spectra. On the basis, some synthesis conditions such as ultrasonic irradiation, pH value of PS emulsion and monomer ratio were optimized. Results indicated that ultrasonic could improve the morphology of microspheres, and acid condition was propitious for deposition of EDOT on the surface of the PS template. With the decreasing of pH value or increasing of monomer ratio, the deposition of PEDOT on surface of PS microspheres increased. When m(EDOT)/m(PS) changed from 0.60 to 1.25, the average particle size of conductive microspheres changed from 1.76 μm to 1.91 μm.