Three-period VO2/SiO2 and VO2/TiO2 multilayers were synthesized on Si(100) monocrystalline substrates with SiO2 and TiO2 buffer, respectively. The X-ray diffraction (XRD) characterization of both multilayers at room temperature showed a well-defined diffraction peak corresponding to the plane Crystallographic (011) strongly suggesting the presence of VO2 (M1) phase. For [VO2/TiO2] x 3, the diffraction peak originated by the crystallographic plane (011), showed a slight shift towards lower values of the angle, relative to the standard peak. The measurements of the electronic transport as a function of temperature for the [VO2/SiO2] x 3 multilayers showed an electrical transition at temperatures of 55 °C and 58 °C and hysteresis (DH), 9 °C and 6 °C, respectively. In the [VO2/TiO2] x 3 system, the electrical transition occurred at 74 °C, with a very narrow hysteresis width (~2 °C). Our results suggest, that the behavior of the hysteresis as well as the displacement shown by the experimental peak of the plane (011), can be interpreted as a consequence of the diffusion of Ti+4 ions to the V+4 sites in VO2 due to the high substrate temperature during deposition. Thus, diffused Ti+4 impurities act as nuclei of phase transformation in the VO2, decreasing the activation energy of the phase transformation, thus explaining the narrowing of observed hysteresis.