Three water insoluble cyclodextrin (CD)-starch copolymers (α-, β-, and γ-CDP) were synthesized by using epichlorohydrin as the crosslink reagent. Comparative study of the kinetic adsorptions of α-, β-, and γ-CDP to astilbin showed that β-CDP had the bestabsorption property. Static equilibrium adsorption studies revealed that β-CDP adsorption capacity rose with the increase of equilibrium concentration of astilbin.And its adsorption capacity decreased with the increase of temperature, which revealed that the adsorption was an exothermic process. Under the conditions of 4 ℃ and equilibrium concentration 360 μg/mL, adsorption capacity of β-CDP to astilbin was 49.52 mg/g. The adsorption could quite fit to the Freundlich adsorption isotherm, indicating that it was the nonuniform, multilayer adsorption. About 91.97% of adsorbed astilbin could be recovered by use of 60% ethanol as the elution solvent. The yield of flavonoids was 2.28% when β-CDP was used for separation and purification of flavonoids from Rhizoma Smilacis Glabrae. The contents of astilbin and total flavonoids were 51.71% and 76.63%, respectively, as determined by HPLC.