Anodic spark deposition (ASD) is an advanced plasma-electrochemical coating process to prepare polycrystalline, ceramic-like conversion coatings on metal surfaces. As an example, polycrystalline barium titanate (BaTiO3) phases have been prepared by the anodic conversion of metal substrate and the metal ions in the electrolyte. By a combination of various characterization techniques, the configuration of the coating was elucidated. On the metal substrate a thin (~50 nm) passivating amorphous film of titania (TiO2) first forms, which subsequently changes to anatase and rutile structures. With increasing anodic potentials, a plasma-chemical conversion reaction starts, leading to the heterogeneous formation of BaTiO3layers of 2–10 μm thickness. The results of this study lead to the formulation of a model describing a polycrystalline and inhomogeneous layer configuration.