Ion-imprinted iodole-functionalized silica-supported (IIS) sorbent was prepared by the hydrothermal-assisted surface imprinting approach. IIS indicated had a high static adsorption capacity of 39.6 mgg(-1) for Sb(III), displayed stable removal efficiency in the range of pH 4-9, offered a rapid removal rate with an equilibrium within 30 min, and could be used repeatedly without a considerable adsorption capacity loss. The IIS sorbent had been successfully applied to solid-phase extraction coupled with hydride generation atomic fluorescence spectrophotometry for the preconcentration and determination of Sb(III) in certified reference materials and real water samples, since recoveries in the range of 97.6%-102.8% were obtained.