Phase transformation of TiO2 from anatase to rutile is studied by UV Raman spectroscopy excited by 325 and 244 nm lasers, visible Rainan spectroscopy excited by 532 nm laser, X-ray diffraction (XRD), and transmission electron microscopy (TEM). UV Raman spectroscopy is found to be more sensitive to the surface region of TiO2 than visible Raman spectroscopy and XRD because TiO2 strongly absorbs UV light. The anatase phase is detected by UV Raman spectroscopy for the sample calcined at higher temperatures than when it is detected by visible Raman spectroscopy and XRD. The inconsistency in the results from the above three techniques suggests that the anatase phase of TiO2 at the surface region can remain at relatively higher calcination temperatures than that in the bulk during the phase transformation. The TEM results show that small particles agglomerate into big particles when the TiO2 sample is calcined at elevated temperatures and the agglomeration of the TiO2 particles is along with the phase transformation from anatase to rutile. It is suggested that the rutile phase starts to form at the interfaces between the anatase particles in the agglomerated TiO2 particles; namely, the anatase phase in the inner region of the agglomerated TiO2 particles turns out to change into the rutile phase more easily than that in the outer surface region of the agglomerated TiO2 particles. When the anatase particles of TiO2 are covered with highly dispersed La2O3, the phase transformation in both the bulk and surface regions is significantly retarded, owing to avoiding direct contact of the anatase particles and occupying the surface defect sites of the anatase particles by La2O3.