Decomposition of metal‐organic precursors to Ba2Ycu3O7‐X films is difficult because of the high reaction temperature required to decompose the BaCO3 intermediate. The recently proposed use of metal trifluoroacetate (TFA) solutions offers an alternative path to barium‐containing superconducting films. The TFA salts decompose to the metal fluorides forming BaF2, eliminating BaCO3 from the system. Ultimate conversion to BYC, however, is shown not only to depend on hydrolysis of the BaF2 at high temperatures, but also hydrolysis of copper trifluoracetate at low temperatures to prevent the volatilization of Cu(TFA)2. These processes result in unique microstructural behavior which can be characterized by electon microscopy and Auger spectroscopy. Effects due to substrate interactions have been eliminated by use of a chemically inert substrate material, BaZrO3.