YBa2Cu3Oy (YBCO) films produced by the ex situ conversion of BaF2-based precursors deposited by physical vapor deposition on ion-beam assisted deposited (IBAD) yttrium-stabilized zirconia (YSZ) and rolling-assisted biaxially textured substrates (RABiTS) templates are characterized by a bi-axially aligned, laminar grain structure that results from the anisotropic growth characteristics of the YBCO phase and its precipitation from a transient liquid phase during the conversion process. A bimodal microstructure characterizes these films and is defined by large, well-formed YBCO grains with Y2O3 precipitates in the bottom region of the film and small YBCO grains with a high density of stacking faults in the upper half. Ba2Cu3Oy or Ba–O–F/CuO second phase layers were often found between large YBCO grains in the bottom half of the films. YBCO grain sizes exceeded 50 μm within the plane of the film in some cases. Conversely, discrete secondary phases of Y2Cu2O5, Y2O3, and Ba2Cu3Oy/Ba–O–F could be found among the much smaller YBCO grains in the top portion of the bimodal structure. The dividing line of the bimodal structure was generally at one half of the film thickness, although exceptions to this trend were found. The highest critical current densities (Jc) and best film alignments for a given film thickness were found in samples where the layers of Ba2Cu3Oy or Ba–O–F were minimized or eliminated from the films. Samples quenched after partial conversion show the segregation of CuO to the top region of the film and the lateral growth of large YBCO grains from a precursor mix of Y2Cu2O5 and Ba–O–F. The data demonstrate that transient liquid phases are part of the conversion process of BaF2-based YBCO films. The control of both CuO segregation and the amount of liquid phases generated during the initial stages of phase formation is needed for optimizing the ex situ conversion process for high-Jc coated conductors.