Hollow mesoporous silica nanospheres with large pore size of around 11 nm have been synthesized by a structural difference based selective etching strategy, and the highly dispersed hydrophobic Fe 3O 4 nanoparticles with a particle size of 5 nm were then impregnated into hollow cores of nanospheres through these large pores by a vacuum impregnation technique. The structural characteristics of obtained magnetic composites were characterized by X-ray diffraction (XRD), Fourier Transform Infrared (FTIR), Transmission Electron Microscopy (TEM), Scanning Electron Microscopy (SEM), Selected Area Electron Diffraction (SAED), Ultraviolet-visible (UV-Vis) and Vibrating Sample Magnetometer (VSM). The results show that the obtained Fe 3O 4-hollow mesoporous silica composites exhibit superparamagnetic property with saturation magnetization value of 4.17 emu/g. Furthermore, the obtained supports show ultrafast immobilization of hemoglobin and the immobilized enzymes are not denatured, indicating that the superparamagnetic hollow mesoporous silica spheres are excellent support for immobilization of enzymes with magnetic recycling property. Copyright