Composite Fe-containing polymer films have been prepared by the plasma-enhanced metal-organic chemical vapor deposition (PEMOCVD), using ferrocene (Cp2Fe) and H-2/Ar as precursor and working gas respectively. The structure and properties of films was characterized by X-ray photoelectron spectroscopy, Auger electron spectroscopy, transmission electron microscopy, transmission electron diffraction, and X-ray diffraction. The electrical and optical properties of the films were also investigated. The results show the films consist of microcrystalline Fe2O3 and Fe-C clusters embedded in an amorphous polymer matrix. The filling factor (f) of Fc affects the structure and properties of films greatly.