Vanadium dioxide (VO2) and vanadium pentoxide (V2O5) thin films change their properties in response to external stimuli such as photons, temperature, electric field and magnetic field and have applications in electronics, optical devices, and sensors. Due to the multiple valence states of V and non-stoichiometry in thin films, it is challenging to grow epitaxial, single-phase V-oxide on a substrate, or a heterostructure of two epitaxial V-oxides. We report the formation of a heterostructure consisting of a few nm thick ultrathin V2O5 epitaxial layer on pulsed laser deposited tens of nm thick epitaxial VO2 thin films grown on single crystal Al2O3(001) substrates without post annealing of the VO2 film. The simultaneous observation of the ultrathin epitaxial V2O5 layer and VO2 epitaxial film is only possible by our unique reflection high energy electron diffraction pole figure analysis. The out-of-plane and in-plane epitaxial relationships are V(2)O(5[)100]parallel to VO2[010]parallel to Al2O3[001] and V2O5[03 (2) over bar]parallel to VO2[100]parallel to Al2O3[1 (1) over bar0], respectively. The existence of the V2O5 layer on the surface of the VO2 film is also supported by X-ray photoelectron spectroscopy and Raman spectroscopy. (C) 2017 Elsevier B.V. All rights reserved.