A novel kind of hyamine-containing crosslinked β-cyclodextrin resin (β-CD-DEAE) was synthesized. 2-Diethylaminoethyl group (DEAE) was introduced on β-cyclodextrin by the reaction of 2-diethylaminoethyl chloride hydrochloride with β-cyclodextrin under basic condition and then the crosslinked resin was formed by the crosslink reaction using epichlorohydrin. The quaternary ammonium group was produced by the quaterisation of DEAE using epichlorohydrin. The new crosslinked cyclodextrin resin was characterized by scanning electron microscopy, Kjeldahl method and infrared spectroscopy. The content of nitrogen approaches approximately 5.55%. Meanwhile, the phenol adsorption property for wastewater treatment has been determined. It was found that the hyamine-containing crosslinked β-CD has a strong capability of phenol adsorption. Under the optimal pH of 9, the adsorbent dosage was 30mg/ml. If the initial phenol concentration was 100mg/l, the maximum phenol adsorption efficiency was 84.42%. In addition, the effective recycling efficiency of the new crosslinked β-CD resin was almost 100%.