Through a novel method, we successfully synthesized electromagnetic (EM) functional polystyrene@polypyrrole@nickel (PS@PPy@Ni) composite microspheres. The PS@PPy spheres with well-defined core/shell structure have been synthesized via an in situ chemical oxidative copolymerization of pyrrole (Py) and N-2-carboxyethylpyrrole (PyCOOH) templated by PS microspheres. The reaction was carried out under heterophase conditions using the mixture of ethanol and water as the continuous phase. Tailored by the carboxyl groups on the surface of microspheres, magnetic nickel layer has been steady deposited onto the P(Py-PyCOOH) layer of the microspheres through an activation-electroless plating technology. The fine PS@P(Py-PyCOOH)@Ni core/shell structures could be obtained with the PyCOOH content up to 50 wt % in the P(Py-PyCOOH) layer. Moreover, the as-prepared PS@P(Py-PyCOOH)@Ni composites are ferromagnetic materials and behave as a good electromagnetic (EM) absorption material due to the coating of Ni layer around the PS@P(Py-PyCOOH) spheres. The PS@P(Py-PyCOOH)@Ni composite spheres show the remarkable EM wave absorption property with the maximum reflection loss (around -20.06 dB) at 10.69 GHz. The EM wave absorption can retained lower than -10 dB within a broad frequency range from 9.16 to 13.75 GHz.