In the present study, Fe3O4@SiO2 core–shell microspheres were prepared via two steps. First, Fe3O4 nanoparticles were synthesized by co-precipitation of Fe+3 and Fe+2 as reaction substrates and NaOH as precipitant. Second, the surface of Fe3O4 was coated with silica by hydrolysis of tetraethylorthosilicate as the silica source. Subsequently, in order to reduce the amount of interaction and the agglomeration of Fe3O4@SiO2 microspheres, the silica shell of these particles was modified by vinyltriethoxysilane as the silane coupling agent. The structural properties of the samples were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and Fourier transform infrared spectroscopy analyses. The results indicated that the average sizes of Fe3O4 and Fe3O4@SiO2 particles were about 50 and 500 nm, respectively. Also, the surface characterization of Fe3O4@SiO2 microspheres showed that the silane coupling agent was covalently coupled with the silica surface.