Abstract: Hollow polyaniline/Fe3O4 microsphere composites with electromagnetic properties were successfully prepared by decorating the surface of hollow polyaniline/sulfonated polystyrene microspheres with various amounts of Fe3O4 magnetic nanoparticles using sulfonated polystyrene (SPS) as hard templates and then removing the templates with tetrahydrofuran (THF). The synthesized hollow microsphere composites were characterized by FT-IR, UV/Vis spectrophotometry, SEM, XRD, elemental analysis, TGA, and measurement of their magnetic parameters. Experimental results indicated that the microspheres were well-defined in size (1.50–1.80μm) and shape, and that they were superparamagnetic with maximum saturation magnetization values of 3.88emu/g with a 12.37wt% content of Fe3O4 magnetic nanoparticles. Measurements of the electromagnetic parameters of the samples showed that the maximum bandwidth was 8.0GHz over −10dB of reflection loss in the 2–18GHz range when the Fe3O4 content in the hollow polyaniline/Fe3O4 microsphere composites was 7.33wt%. [Copyright &y& Elsevier]