A composite of porous Fe3O4 hollow microspheres/graphene oxide (Fe3O4/GO) has been fabricated through a facile self-assembly approach. Driven by the mutual electrostatic interactions, the amine-functionalized Fe3O4 microspheres prepared by a hydrothermal method and then modified by 3-aminopropyltrimethoxysilane were decorated with negatively-charged GO sheets. The Fe3O4 microspheres were hollow with porous surfaces and the surfaces were successfully modified with the amine, which was confirmed by Fourier transform infrared spectroscopy. The specific saturation magnetization of Fe3O4/GO was 37.8 emu g−1. The sorption performance of Fe3O4/GO for Cr(VI) was evaluated. The maximum sorption capacity for Cr(VI) on Fe3O4/GO was 32.33 mg g−1, which was much higher than that of Fe3O4 microspheres. The GO sheets could not only prevent agglomeration of the Fe3O4 microspheres and enable a good dispersion of these oxide microspheres, but also substantially enhance the specific surface area of the composite. The Fe3O4/GO composite may be a promising sorption material for the separation and preconcentration of heavy metal ions from aqueous solutions in environmental pollution cleanup.