We describe the conversion of yttrium, barium, and copper trifluoracetate-derived solid precursors to epitaxial YBa 2 Cu 3 O x superconducting ceramics on (001)-oriented LaAlO 3 substrates. Transmission electron microscopy, electron energy loss spectroscopy, energy-dispersive X-ray analysis, and X-ray diffraction are used to characterize the reaction path and nucleation mechanism yielding high critical current YBa 2 -Cu 3 O 7 . Our results show that the pyrolysis of the trifluoracetate solutions yields a nanostructured, partially amorphous Ba 1-x Y x F 2+x matrix having a Ba/Y ratio close to 2, with homogeneously dispersed CuO nanoparticles. Upon heating, the chemical trajectory of the fluoride matrix and the overall microstructural evolution of the ceramic precursor prior to YBa 2 Cu 3 O 7 nucleation is driven by the decomposition and oxidation of this solid solution. The Y solid solubility decreases with temperature yielding Y 2 O 3 which reacts with the CuO particles forming Y 2 Cu 2 O 5 at about 700°C. In addition, electron energy loss spectroscopy reveals a high oxygen concentration and almost no Y in the matrix quenched from 795°C, at a stage where the YBa 2 Cu 3