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Polystyrene/polyaniline core-shell structure microspheres were synthesized in the presence of poly(sodium 4-styrenesulfonate) as stabilizer and hydrochloric acid as dopant to improve the processibility of conducting polyaniline. After the one-pot reacting process, the product was easily purified by washing with water. The polyaniline shell covering the polystyrene sphere surface was confirmed with FT-IR and X-ray photoelectron spectroscopy. The conductivity of the polyaniline-coated polystyrene particles was 0.0017 S/cm and increased to 0.1 S/cm after being doped in the Hel vapor. The morphology of the microspheres was characterized by TEM and SEM. The particles show a more uniform and smooth surface than previous particles.