Sea urchin-like Fe3O4/Metal-Silicate hollow spheres were fabricated via an in situ chemical conversion route. The Fe3O4/Metal-Silicate composites exhibit both hollow structures and superparamagnetism. The BET surface area of the Fe3O4/CuSilicate can be easily adjusted. Fe3O4/CuSilicate exhibited an excellent adsorption capacity on high abundant proteins in human blood.