Vanadium films were deposited on Si(100) substrates at room temperature by direct current (DC) magnetron sputtering. The microstructure and surface morphology were studied using scanning electron microscopy (SEM) and atomic force microscope (AFM). The oxidation resistance of films in air was studied using X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The results showed that the amorphous vanadium film with a flatter surface had higher oxidation resistance than the crystalline film when exposed to atmosphere. The rapid formation of the thin oxide layer of amorphous vanadium film could protect the film from sustained oxidation, and the relative reasons were discussed.