Zirconium clusters of UiO-66 have been hydroxylated with NaOH to generate strong binding sites for As(III) species in wastewater treatment. Hydroxylated UiO-66 provides high adsorption capacity over a wide range of pH from 1 to 10 with a maximum uptake of 204 mg g-1, which is significantly enhanced compared to those of pristine UiO-66, acid-modulated UiO-66, and other adsorbents for use in a wide pH range of treatment processes. The local structure of hydroxylated sites and As(III) adsorption mechanism are determined by extended X-ray absorption fine structure combined with density functional theory calculations.