In this work, TiO2 nanoparticles with exposed (001) facets, mixed-phase and particle size as small as similar to 20 nm were prepared via solvothermal process by using mixture of water and acetic anhydride as solvent and HF as shape directing agent. The as prepared TiO2 was characterized by X-ray diffraction (XRD), electron microscopes, elemental analysis (EA) and X-ray fluorescence (XRF), thermalgravimetric analysis and differential scanning calorimetry (TG-DSC), and nitrogen adsorption/desorption isotherms. The results indicated that the uncalcined sample which obtained after solvothermal process contained amorphous carbon, TiOF2, H2Ti2O5 center dot H2O, and Ti-containing organometallic compound. When calcined at temperature lower than 750 degrees C, a mixture of anatase and rutile was obtained. The photocatalytic activity of as prepared TiO2 was tested as H-2 evolution rate from water containing methanol as sacrificial agent. The photocatalytic activity for TiO2 prepared by using H2O/Ac2O as solvent was about 6 times higher than that of sample prepared by using HAc as solvent. The H-2 evolution rate over TiO2 sample prepared under optimum condition was 7.65 mmol.g(-1).h(-1), which was almost 50% higher than that of commercial P25. The influence of solvent, solvothermal temperature and calcination temperature on the morphology, particle size, phase composition and photocatalytic activity of as-synthesized TiO2 was discussed in detail. (C) 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.