Mesoporous aluminium magnesium oxide composites with varying composition (Mg content: 0-100%) and high surface area (118-425 m(2) g(-1)) are synthesized by a facile, low-cost and scalable sol-gel method. The mesostructure and crystallinity are controlled by varying the composition and calcination temperature. The mesopores evolve from hexagonally ordered to wormhole-like in structure with increasing Mg/Al ratio. The mesoporous aluminium magnesium oxide composites are highly efficient adsorbents for removing As(V) and As(III) from water. The mesoporous magnesium oxide shows unprecedentedly high adsorption capacities of 912 mg g(-1) for As(V) at pH 3 and 813 mg g(-1) for As(III) at pH 7 with a dose of 0.5 g L-1; significantly higher than those of reported adsorbents. Exceptional adsorption capacities for arsenic are retained over a wide pH range, and high selectivity for As(V) is realized even in the presence of co-existing anions. The arsenic adsorption performance correlates to the properties of the composites including the Mg/Al ratio, point of zero charge, crystallinity and mesostructure. The arsenic adsorption mechanism is elucidated. Due to their high surface areas, large pore volumes, tunable mesopore structures and high quantities of accessible hydroxyl groups with strong chemisorption binding affinity to arsenic, as well as extremely high adsorption capacities and selectivity, these mesoporous aluminium magnesium oxides are promising adsorbent candidates for the remediation of arsenic in water.