Pressurized water extraction followed by sub/supercritical methanol drying was used for synthesis of TiO2 from gels prepared by sol-gel technique using Triton X-114 like template. It was proved that pressurized water causes titania crystallization. Subsequent sub/supercritical methanol drying is responsible for total elimination of the rest of organic phase originating from the template. The impact of temperature and pressure modifications on titania purity was more essential for pressurized water extraction. The specific surface area significantly increases with removal of the residual organic phase. Anatase was a dominant crystalline phase. The fraction of minor brookite was in the range 20-30 wt.%. In situ XRD showed stability of titania crystallites size up to 300 degrees C and the presence of brookite crystallites even up to 600 degrees C. The correlation between Raman FWHM and XRD crystallite size was not influenced by the presence of organic phase and was more sensitive for anatase E-g band 647 cm(-1). (C) 2012 Elsevier Ltd. All rights reserved.