Vanadium oxide films were grown by atomic layer deposition using the tetrakis[ethylmethylamino] vanadium as the vanadium precursor and H2O as the oxide source. The effect of the source temperature on the quality of vanadium oxide films and valence state was investigated. The crystallinity, surface morphology, film thickness, and photoelectric properties of the films were characterized by x-ray diffraction, atomic force microscope, scanning electron microscope, I–V characteristics curves, and UV–visible spectrophotometer. By varying the source temperature, the content of V6O11, VO2, and V6O13 in the vanadium oxide film increased, that is, as the temperature increased, the average oxidation state generally decreased to a lower value, which is attributed to the rising of the vapor pressure and the change of the ionization degree for organometallics. Meanwhile, the root-mean-square roughness decreased and the metal–insulator transition temperature reduced. Our study is great significance for the fabrication of vanadium oxide films by atomic layer deposition.