Experimental conditions for the sol-gel synthesis of TiO2 were modified by using Polyethylene glycol (PEG) as well as an addition of acid catalyst. Synthesis of brookite and mixed brookite with rutile was obtained. X-ray powder diffraction and Micro Raman measurements confirmed the crystallization of brookite while using pure PEG4000 with low molar acid concentration and a mixed brookite with rutile phase for PEG4000 with high molar acid concentration. High Resolution Transmission Electron Microscopic analysis revealed the presence of nanocrystalline assembly with sizes between 8 and 16xA0;nm. Direct phase transition from brookite to rutile phase was observed during the further heat treatment of brookite sample.