We are developing electrically insulated coatings for the liquid-metal/structural-material interface of the breeder blanket for magnetic fusion reactors. Our earlier experimental studies indicated that sintered Y2O3 is compatible with liquid Li. In continuing studies, we have deposited thin (0.2 and 0.8 μm) yttrium films on V-4Cr-4Ti structural material by physical vapor deposition (PVD). Annealing the thin Y-metallic PVD film on O-charged V-4Cr-4Ti at 750°C for 17 h formed an oxide film by the solid-state reaction between O and Y. Both energy dispersive spectroscopy (EDS) and X-ray diffraction indicated that the Y-metallic films converted to either YVO3 or Y8V2O17 after annealing. When these samples were exposed in 2.8 at.% Ca-Li at temperatures of 700°C for 99 h, a uniformly microstructured CaO layer was formed on the top of the Y-V oxides, but localized Y was not detected by cross-sectional EDS analysis. The addition of Si was found to minimize the V incorporation in the in-situ forming film.