A hydroxyl-rich layer forms on the surface of TiO 2 by simple ball milling in aqueous medium. This layer facilitates the surface adsorption of the rhodamine B (RhB) molecules and yields a notable Vis-light photocatalytic activity for RhB decomposition in aqueous solution, demonstrating the efficiency of the simple milling process to impose the notable Vis-light activity. It has been interpreted that Vis-light-excited RhB loses electrons to the surface hydroxyl group more suitably to form RhB + , while dissolved oxygen takes electrons more suitably to form an O 2 - * radical, thereby yielding the notable Vis-light photocatalytic activity by the surface photosensitization.