Highly oriented VO2(B), VO2(B) + V6O13 films were grown on indium tin oxide glass by radio-frequency mag-netron sputtering. Single phase V6O13 films were obtained from VO2(B) + V6O13 films by annealing at 480℃C invacuum. The vanadium oxide films were characterized by x-ray diffraction and x-ray photoelectron spectra (XPS). Itwas found that the formation of vanadium oxide films was affected by substrate temperature and annealing time, be-cause high substrate temperature and annealing were favourable to further oxidation. Therefore, the formation of highvalance vanadium oxide films was realized. The V6O13 crystalline sizes become smaller with the increase of annealingtime. XPS analysis revealed that the energy position for all the samples was almost constant, but the broadening ofthe V2p3/2 line of the annealed sample was due to the smaller crystal size of V6O13.