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The structural characteristics and optical property of TiO₂ powders with different phases are studied by various techniques in this paper. Butyl titanate and oxalic acid were used as Ti source and catalyst, respectively, for sol–gel synthesis of TiO₂ powders. The synthesized products were characterized by X-ray diffraction, transmission electron microscopy, differential scanning calorimetry, thermogravimetric analysis and photoluminescence techniques. X-ray diffraction patterns confirm TiO₂ phase transformation from amorphous to anatase and rutile with the increase in calcination temperatures from 200 °C to 700 °C. Two exothermic peaks at 275 °C and 485 °C on the differential scanning calorimetry curve are responsible for the decomposition of the oxalate groups, which can enhance TiO₂ phase transformation from amorphous to anatase and rutile. The crystalline sizes of the synthesized TiO₂ powders are in the …