The conditions leading to the Donnan membrane equilibrium arise from the inability of ions to diffuse out from one phase in a heterogeneous system. In a polymeric cation exchanger, negatively charged sulfonic acid groups are covalently attached to the polymer chains, and thus, they cannot permeate out of the polymer phase. Conversely, a polymeric anion exchanger contains a high concentration of non-diffusible positively charged quaternary ammonium functional groups. It is well-established that submicron or nanoscale hydrated iron(III) oxide (HFO) particles exhibit high sorption affinity toward both arsenates and arsenites. In this study, commercially available cation and anion exchangers were used as host materials for dispersing HFO nanoparticles within the polymer phase using a technique previously developed. The resulting polymeric/inorganic hybrid sorbent particles were subsequently used for arsenic removal in the laboratory. The most significant finding of the study is that the anion exchanger as a substrate containing dispersed HFO offered substantially higher arsenate removal capacity as compared to the cation exchanger, all other conditions remaining identical. In fact, HFO nanoparticles dispersed within the gel-type cation exchanger were unable to remove arsenic. The Donnan membrane effect resulting from the nondiffusible negatively charged sulfonic acid groups in the cation exchanger did not allow permeation of arsenate into the polymer phase (i.e., arsenate was excluded from the spherical beads dispersed with HFO nanoparticles). On the contrary, anion-exchanger-supported HFO particles or HAIX offered very high arsenic removal capacity; less than 10% of influent arsenic broke through after 10 000 bed vol. HAIX was also amenable to efficient regeneration with 2% NaOH and 3% NaCl and capable of simultaneously removing both perchlorate and arsenic selectively. According to the information in the open literature, HAIX is the first hybrid sorbent that utilizes the Donnan membrane effect of the host material for sorption enhancement. From a generic viewpoint, other metal oxide/metal nanoparticles may also be judiciously embedded in appropriate support materials that would reject or enhance permeation of targeted ionic solutes.