Molecularly imprinted polymers (MIPs), based on photografting surface-modified polystyrene beads as matrices, were prepared with acrylamide as the functional monomer, bovine hemoglobin as the template molecule and N, N’-methylene bisacrylamide as the crosslinker in a phosphate buffer. The results of IR, scanning electron microscope (SEM) and elemental analyses demonstrated the formation of a grafting polymer layer on the polysty-rene-bead surface. Subsequent removal of the template left behind cavities on the surface of the polymer matrix with a shape and an arrangement of functional groups having complementary binding sites with the original tem-plate molecule. The adsorption studies showed that the imprinted polymers have a good adsorption capacity and specific recognition for bovine hemoglobin as the template molecule. Our results demonstrated that the polymer prepared via the photografting surface-modified method exhibited better selectivity for the template. Attempts to employ the new method in molecular imprinting techniques may introduce new applications for MIPs and facilitate probable protein separation and purification.