Titanium dioxide (TiO2) submicrospheres (SMs) have been successfully synthesized via a solvothermal method by hydrolysis of tetrabutyl titanate in ethanol solution with the cetyltrimethylammonium bromide (CTAB) presented. The SMs are composed of closely packed rod or tetragonal nanoparticles (NPs), and the inner structure of SMs depends on whether the hexamethylenetetramine (HMTA) was introduced in the reaction or not. The surface and inner morphologies, structure, and optical properties of the SMs were investigated.