Abstract: The pure hexagonal ZnTiO₃ powders were prepared by sol-gel process using tetrabutyl titanate (Ti (OC₄H₉)₄), zinc nitrate hexahydrate (Zn (NO₃)₂·6H₂O), anhydrous ethanol (CH₃CH₂OH) and glacial acetic (CH₃COOH) as the raw materials. The thermal behavior and phase transformation of the precursor xerogel were investigated by thermogravimetry and differential thermal analysis (TG-DTA) and X-ray diffraction (XRD). The crystalline phase, morphology and grain size of the powders were characterized by XRD and field emission scanning electron microscope (FE-SEM). The thermal behavior of precursor xerogel was divided into three stages in the TG-DTA analysis. The first stage was below 262 ℃ with the decomposed organic solvents. Amorphous cubic ZnTiO₃ was obtained at the second stage at about 262~700 ℃, and hexagonal ZnTiO₃ appeared at the last stage, i.e.700~900 ℃. The purity hexagonal ZnTiO₃ powders can be prepared by heat treatment at 700~900 ℃ for 2 h of the precursor xerogel, which was obtained by the sol reaction at 60 ℃.