The advantages of Thermo-Raman spectroscopy are the identification of structure and the ability to monitor the transformation of a sample in a heating process. In this work, Raman spectra were taken continuously from xerogel TiO2 in a heating process similar to that in TGA/DTA. The variation in Raman spectra showed the phase transformation from xerogel to amorphous TiO2 and then to anatase and rutile successively was consistent with the peaks in TGA for a weight loss of 25% at 82 degrees C and two extra endothermic peaks in DTA at 382 and 573 degrees C. However, the transformation from anatase to rutile at 573 degrees C was not complete.