Porous TiO2 (anatase) with bimodal pores (50 and 430 nm) and monomodal pores (50 nm) was synthesized by using colloidal crystals as templates. Electrochemical capacity of lithium insertion/extraction to the bimodal porous TiO2 was as large as 66.1 mAh.g(-1) at the current density of 3.7 A.g(-1), which was higher than those of nanoparticulate TiO2 and porous TiO2 prepared by using 50 nm PS colloid.