The introductory part reviews the impact of thin film fabrication, precipitation versus vacuum-based methods, on the initial defect state of the material and microstructure evolution to amorphous, biphasic amorphous-nanocrystalline, and fully nanocrystalline metal oxides. In this study, general rules for the kinetics of nucleation, crystallization, and grain growth of a pure single-phase metal oxide thin film made by a precipitation-based technique from a precursor with one single organic solvent are discussed. For this a complete case study on the isothermal and non-isothermal microstructure evolution of dense amorphous ceria thin films fabricated by spray pyrolysis is conducted. A general model is established and comparison of these thin film microstructure evolution to kinetics of classical glass-ceramics or metallic glasses is presented. Knowledge on thermal microstructure evolution of originally amorphous precipitation-based metal oxide thin films allows for their introduction and distinctive microstructure engineering in devices-based on microelectromechanical (MEMS) technology such as solar cells, capacitors, sensors, micro-solid oxide fuel cells, or oxygen separation membranes on Si-chips.