Flavonoids are the main bioactive components responded for the health promoting effects of Rhizoma Smilacis Glabrae ( RSG ), an herbal material used in many functional food of China. An eco‐friendly method with β‐cyclodextrin (β‐CD)‐assisted extraction and resin adsorption/desorption was developed for total flavonoids purification from RSG . Because of complexes formation between flavonoids and β‐CD, aqueous solution was used for extraction instead of ethanol. The CD‐assisted extraction was optimized through defining optimal CD species, concentration, extraction temperature, and time. The adsorption property of eight macroporous resins on astilbin was compared by adsorption kinetics and capacity. All resins could reach the adsorption equilibrium within 2 hr. Further analyzed by Langmuir and Freundlich models, H103 resin with the best adsorption capacity was selected. The desorption property of different ethanol–water solution was compared. Results showed that by using 75% ethanol, astilbin could be well desorbed from the resin with the recovery of 96.3%. Because of complexes formation, the presence of β‐CD would slightly decrease the adsorption rate and capacity of H103 with concentration dependent. In dynamic adsorption, decreasing the flow rate could minish the effects of β‐CD. The developed method was successfully used for total flavonoids purified from RSG . The yield of purified product was 8.78%, with astilbin and total flavonoids content of 363.8 and 505.7 mg/g, respectively. The purity was 1.74 times increased with the recovery of 94.38% compared with the extract obtained directly through 50% ethanol extraction.