Micro-sized TiO2 cage consisted of anatase nanopartides on the edges of each cube, was synthesized using TTIP as the reagent and NaF submicrometer sized cubes as the template. When a salt of cube was adopted as the template, the reactants prefer to grow on the active sites, edges and corners of the cube, after removing the NaF template, the skeleton of the cube remain as the cage-shaped materials. The hierarchical structures with nano-sized anatase particles and micro scaled cage architecture markedly enlarge the surface area and enhance the light harvesting by light scattering of TiO2 frame, resulting in great photo-catalytic performance, which leads to the photo-degradation of methylene blue by 40% higher than that was achieved by crushed nanoparticles. (C) 2013 Elsevier B.V. All rights reserved.