The PSt-g-PVAc microspheres were obtained by dispersion copolymerization of styrene(St) and PVAc macromonomer with a vinylbenzyl end group.And diameters of the PSt-g-PVAc microspheres are 500-700 nm.PSt-g-PVA composite microspheres were derived from alkaline hydrolysis from PSt-g-PVAc microspheres.The functional microspheres were prepared via the nucleophilic reaction between PSt-g-PVA microspheres and Cibacron Blue F3GA(CB).The biggest amount of CB on surfaces of the functional microspheres was 139.22 μmol/g which measured by using an elemental analysis instrument.The amount of HSA adsorption on functional microspheres was 40.9 mg/g.The highest desorption ratio(92.11%) was achieved by using an eluent of 0.5 mol/L NaSCN(pH 8.0).The functional microspheres could be reused without significant decreases in the adsorption capacities.