A novel surface imprinting method on macroporous SiO2 microspheres with highly ordered three-dimensional interconnected structure has been developed for bovine hemoglobin (BHb) protein recognition. The selective experiment showed that the synthesized macroporous microspheres exhibited good specific recognition for template molecules. Compared with the traditional bulk imprinted polymers, the surface imprinting microspheres showed higher binding kinetic behavior, and its binding rate constant was nearly about 7 times as large as that of the bulk imprinted polymers.