Epitaxially grown, chemically homogeneous yttria-stabilized zirconia thin films (“YSZ”, 8 mol% Y2O3) are prepared by direct-current sputtering onto a single-crystalline NaCl(0 0 1) template at substrate temperatures ≥493 K, resulting in unsupported YSZ films after floating off NaCl in water.A combined methodological approach by dedicated (surface science) analytical characterization tools (transmission electron microscopy and diffraction, atomic force microscopy, angle-resolved X-ray photoelectron spectroscopy) reveals that the film grows mainly in a [0 0 1] zone axis and no Y-enrichment in surface or bulk regions takes place. In fact, the Y-content of the sputter target is preserved in the thin films. Analysis of the plasmon region in EEL spectra indicates a defective nature of the as-deposited films, which can be suppressed by post-deposition oxidation at 1073 K. This, however, induces considerable sintering, as deduced from surface morphology measurements by AFM.In due course, the so-prepared unsupported YSZ films might act as well-defined model systems also for technological applications.