In the present study a novel technique was proposed to prepare a polymer-supported hydrated ferric oxide (D201-HFO) based on Donnan membrane effect by using a strongly basic anion exchanger D201 as the host material and FeCl3-HCl-NaCl solution as the reaction environment. D201-HFO was found to exhibit higher capacity for arsenic removal than a commercial sorbent Purolite ArsenX. Furthermore, it presents favorable adsorption selectivity for arsenic removal from aqueous solution, as well as satisfactory kinetics. Fixed-bed column experiments showed that arsenic sorption on D201-HFO could result in concentration of this toxic metalloid element below 10 μg/L, which was the new maximum concentration limit set recently by the European Commission and imposed by the US EPA and China. Also, the spent D201-HFO is amenable to efficient regeneration by NaOH-NaCl solution.