A new protein imprinted polymer was prepared on silica surface modified with vinyltrimetho xysilane, using acrylamide as the functional monomer, N,N-methylene bisacrylamide as the cross linker and modified polyvinyl alcohol (PVA) as the assistant recognition polymer chains (ARPCs). The framework of ARPCs was analyzed by the infrared spectrum (IR). Scanning electron microscopy (SEM) images demonstrated the different morphologies. The effect of ARPCs contents on the MIP absorption ability was investigated. The study of adsorption kinetics showed that the adsorption capacity of molecularly imprinted polymers (MIPs) was obviously improved when ARPCs were introduced into the polymer matrix. Competitive adsorption experiments were used to investigate the selectivity to the template bovine hemoglobin (BHb) from the mixture of other proteins. The sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) results showed that MIPs had excellent specific adsorption ability to the template BHb.