A method of electroforming Zr metal, Zr-Al alloy and carbon film on ceramic substrates has been developed. Using this method, it is possible to apply these films to ceramic substrates, which are complicated in structure. Zr metal and alloy film are formed in the LiCl-KCl melt containing Zr(II), whereas carbon film is formed in the molten carbonate. The electrode consists of a metal part and the ceramic substrate. The films develop between the metal part and the ceramic substrate and propagate along the surface. To form the film there has to be sufficient initial current density to deposit dendritic Zr, carbon whiskers or cubic carbon particles on the metal part.