Fluorocarbon films were deposited on type 301 stainless steel substrates from mixtures of hexafluoroetbane (HFE) or hexafluoroacetone (HFA) and acetylene and argon in a radio-frequency (13.56 MHz) plasma discharge. A 10 nm thick polysilicon interlayer was deposited prior to fluorocarbon film deposition to obtain good adhesion. To prevent film failure, a-C:H layer was deposited on the polysilicon layer prior to fluorocarbon film deposition, resulting in a-C:H/fluorocarbon composite film structures. The influence of the feed gas composition on the properties of the layered structure was investigated. Surface energies of the films were calculated from the film contact angle values obtained with water and diiodomethane. The composition of the surface layer of these films was characterized using X-ray photoelectron spectroscopy (XPS). The resistance offered by these a-C:H/fluorocarbon film structures to anodic breakdown in an electrolyte containing 0.1 M NaCl and 0.1 M Na2SO4 was studied using a potentiostatic technique. The anodic current density for the coated type 301 stainless steel samples was at least 3 orders of magnitude smaller than that for the bare sample and more than an order of magnitude smaller than that observed with samples coated with only the (equally thick) a-C:H layer. The resistance offered by the layered coatings to solution penetration increased with increasing fluorine content in the films.