This paper evaluates the arsenic adsorption characteristics of a macroporous polymer coated withcoprecipitated iron–aluminium hydroxides (MHCMP). The MHCMP adsorbent-composite fits best witha pseudo-second order model for As(III) and a pseudo-first order kinetic model for As(V). The MHCMPshows a maximum adsorption capacity of 82.3 and 49.6 mg As/g adsorbent for As(III) and As(V) ionsrespectively, and adsorption followed the Langmuir model. Extended X-ray absorption fine structureshowed that binding of As(III) ions were confirmed to take place on the iron hydroxides coated on theMHCMP, whereas for As(V) ions the binding specificity could not be attributed to one particular metalhydroxide. As(III) formed a bidentate mononuclear complex with Fe sites, whereas As(V) indicated on abidentate binuclear complex with Al sites or monodentate with Fe sites on the adsorbent. The columnexperiments were run in a well water spiked with a low concentration of As(III) (100 g/L) and a commer-cially available adsorbent (GEH®102) based on granular iron-hydroxide was used for comparison. It wasfound that the MHCMP was able to treat 7 times more volume of well water as compared to GEH®102,maintaining the threshold concentration of less than 10 g As/L, indicating that the MHCMP is a superioradsorbent.