Although Fe-chitosan adsorbents are attractive for removing arsenite from water, the practical applications of these granular adsorbents are mainly limited by slow adsorption kinetics. In this study, radially porous Fe-chitosan beads (P/Fe-CB) were prepared using freeze-casting technique. The P/Fe-CB particles possess radially aligned micron-sized tunnels from the surface to the inside as well as excellent acid resistance. Kinetic studies show that the adsorption equilibrium time of P/Fe-CB to 0.975 mg/L As(III) (within 240 min) is considerably shorter than that of compact Fe-chitosan beads (over 600 min). The maximal adsorption capacity of P/Fe-CB for As(III) is 52.7 mg/g. It can work effectively in a wide pH range from 3 to 9, and the coexisting sulfate, carbonate, silicate and humic acid have no significant effect on As(III) removal. The addition of H2O2 can further accelerate and promote the As(III) removal except at high pH (11) and phosphate concentration (50 mg/L). The fixed-bed experiments demonstrate that the P/Fe-CB column can effectively treat about 3000 bed volume (BV) of simulated As(III)-containing groundwater to meet the drinking water standard ( < 10 mu g As/L). This study would extend the potential applicability of porous Fe based chitosan adsorbent and millimeter-sized adsorbent combined with H2O2 to a great extent.