Almost stoichiometric YBa2Cu3O7-δ(110) or (103) and SrTiOx(110) films, and multilayer films consisting of them have successfully been grown epitaxially on hot SrTiO3 substrates by 90off-axis rf magnetron sputtering with facing targets. Their whole composition, compositional distribution in depth, crystallinity and surface morphology were examined by inductively coupled plasma spectroscopy, Auger electron spectroscopy, reflection high-energy electron diffraction, and scanning tunneling microscopy or atomic force microscope, respectively. When any YBa2Cu3O7-δ film was exposed to air after deposition, a Ba-rich layer was formed in a near surface region of the film. However, such a compositional distribution in depth of the film was improved by in situ deposition of a SrTiOx film on it. Moreover, the surface roughness of the YBa2Cu3O7-δ film was improved by predeposition of a SrTiOx film under it. On the basis of these results, both YBa2Cu3O7-δ/SrTiOx/YBa2Cu3O7-δ/SrTiO3(sub.) and YBa2Cu3O7-δ/SrTiOx/YBa2Cu3O7-δ/SrTiOx/SrTiO3(sub.) multilayer films with average surface roughness of 3 nm were grown reproducibly, which had uniform compositional distribution throughout the depth of the film except a near surface region of the top YBa2Cu3O7-δ layer. A new 222 structure described by Sr8Ti8O20 (Sr2Ti2O5) with a long range ordered arrangement of oxygen vacancies was formed in the SrTiOx films deposited epitaxially on YBa2Cu3O7-δ films.