A method of forming a primary coat, which consists of a V- or Ti-containing film, formed on the surface of a subject on which holes or the like have been formed, according to the CVD technique, while using, for instance, a tetravalent amide-type vanadium-containing organometal compound as a raw gas and using, for instance, tertiary butyl hydrazine as a reducing gas, and a copper-containing film is then formed on the primary coat, according to the CVD technique, to thus fill the holes or the like with the copper-containing film and to thus form copper distributing wire, which is excellent in the hole-filling properties and excellent in the adhesion to a primary coat, this process can be applied to the field of copper distributing wires used in the semiconductor industries.