We have found out that vacuum exposure of YBa2Cu3O7‒δ thin epitaxial films at 300 K for 24 hours decreases oxygen content and induces changes in their crystal structure depending on the films synthesis conditions. YBa2Cu3O7‒δ films on SrTiO3 (100) substrates were synthesized by pulsed laser deposition. The crystal structure was studied using XRD technique. Additional maxima of diffraction peak (005) before and after vacuum exposure indicate the presence of regions with different oxygen content; and the change in the shape of the rocking curves indicate a change in the crystallites orientation. After vacuum exposure, the oxygen deficiency δ in the films increased from ~0.01 to 0.6 for films with a crystallites size of 2-10 nm and from ~0.25−0.35 to 0.6 for crystallites size of 500−1000 nm. The appearance of a residual resistance after the superconducting transition in the dependence R(T) may be explained by the fact that oxygen loss mainly in the boundary regions of the crystallites takes place, so that their boundaries become dielectric, while the crystallites themselves remain superconductive. Based on the data of X—ray diffraction analysis, as well as resistive measurements, we have come to the conclusion about oxygen loss through grain boundaries in films with nanocrystallites of 2-10 nm in size, and also through structural defects in films with larger crystallites.