TiO2 micro/nanospheres were synthesized by a combination process contains hydrolysis of titanium tetra-n-butyl in mixed solution of anhydrous ethanol/ammonia and the subsequent calcination under 550 degrees C for 7 h. The pH values of the mixed solution were tuned to be 10.4, 11.0 and 11.6, respectively, by adding different amounts of ammonia. Scanning electron microscope (SEM) and transmission electron microscope (TEM) were used to characterize the morphologies and the crystallinity. X-ray diffraction (XRD) patterns indicated that pH value of the precursors has an important effect on the crystal phase composition. UV-vis diffuse reflectance spectrum was applied to characterize the optical properties of samples. Degradation of methylene blue under the irradiation of 300W Hg lamp confirmed the enhanced photocatalytic activity of TiO2 micro/nanospheres. In addition, the formation mechanism was proposed. (C) 2011 Elsevier B.V. All rights reserved.