Various porous titania photocatalysts are analyzed three-dimensionally in real space by electron tomography. Shapes and three-dimensional (3D) distributions of fine pores and silver (Ag) particles (2 nm in diameter) within the pores are successfully reconstructed from the 3D data. Electron tomography is applied for measuring the specific surface area of the porous structures including open and closed porosity. Calculated specific surface areas of 22.8 m2/g for a conventional sol-gel TiO2 sample and 366 m2/g for a highly porous TiO2 sample prepared using the Pluronic P-123 self-assembly process are compared with those measured by the general BET method. The real-space surface measurement indicates that the highly porous TiO2 produced by the present method using block copolymers has a greater number of effective reaction sites for the degradation of methylene blue. Electron tomography shows a great potential to contribute considerably to the nanostructural analysis and design of such catalyst materials for photocatalysis.