After hollow microspheres (HM) were surface modified, a layer of electromagnetic polyaniline/Fe3O4 composite (PAN/Fe3O4) was successfully grafted onto the surface of the self-assembled monolayer coated HM, resulting in HM/PAN/Fe3O4 composites. In this approach, gamma-aminopropyltriethoxy silane was adopted to form a well-coating monolayer with amino groups for the graft polymerization of aniline, which played an important role in fabricating the core-shell structure. FeCl3 was used as the oxidant not only for aniline to form PAN, but also for FeCl2 to prepare the magnets. The structure, morphologies, and magnetic properties of the as-prepared samples were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction and vibrating sample magnetometer. The results indicated that the HM/PAN/Fe3O4 composites possess low density (rho < 1.0 g/cm(3)), controllable morphology, and good magnetic properties at room temperature (saturation magnetization Ms = 8.32 emu g(-1) and coercive force Hc approximate to 0). Crown Copyright (C) 2011 Published by Elsevier B.V. All rights reserved.