Preparation of TiO2 mixed with PEG has been carried out using sol-gel synthesis. PEG addition promotes the particulate morphology and its 3D assembly. PEG addition promotes the brookite phase formation upon crystallization. 3D macroporous with mesoporosity of pore sizes from 3.32 nm to 12.54 nm obtained. Complete phase transition from brookite to anatase was observed at 444 °C.