YBa2Cu3O7−δ (YBCO) films were fabricated via a fluorine‐free metal organic deposition (MOD) method followed by high‐temperature, low oxygen partial pressure annealing. Trimethyl acetate salts of copper, yttrium, and barium hydroxide were used as the precursors, which were dissolved in proponic acid‐ and amine‐based solvents. After spin‐coating and burnout, samples were annealed at 740°C in 180 ppm oxygen partial pressure and exposed to humid atmosphere for different times. A critical transition temperature, Tc(R=0) of 90.2 K and a transport critical current density (Jc) of 0.55 MA/cm2 (77 K and self‐field) were obtained for 0.2 μm YBCO films on CeO2‐buffered yttria‐stabilized zirconia (YSZ) substrates. X‐ray studies shows that the YBCO films have sharp in‐plane and out‐of‐plane texture for all samples; however, the porosity of the YBCO film varies with the time of exposure to the humid atmosphere. A reaction between YBCO and CeO2 during the high‐temperature anneals and formation of the reaction product BaCeO3 was confirmed by X‐ray diffraction (XRD) studies. The XRD and transmission electron microscopy analysis indicated that the epitaxial relations in the film were YBCO (00l)//CeO2 (00l)//YSZ (00l) and YBCO [100]//CeO2 [110]//YSZ [110].