A series of anatase phase Fe-doped TiO2 nanoparticles are prepared by a modified sol-gel method. Spontaneous Raman spectroscopy is utilized to characterize the crystal structures of these nanoparticles and investigate their structural transformation under the exposure of a 532 nm green laser. The anatase phase of TiO2 can be effectively converted into the rutile phase with the assistance of Fe doping. It is found that the critical laser intensity for phase transformation decreases with increasing the Fe content. We ascribe this tendency to the enhanced optical absorption and the photo-induced thermal heating effect, which can be associated with the defect structure within the bandgap of Fe- TiO2 nanoparticles. Our study demonstrates an all-optical approach to pump and probe the phase transformation of metal-doped TiO2 nanoparticles.