Polyelectrolyte multilayers (PEMs) fabricated by the layer-by-layer adsorption of cation and anion polyelectrolyte solution are used to modify the properties of the substrate and to improve adhesion for electroless plating. In this paper, a fabrication process of specific membrane that consists two kinds of polyelectrolytes adsorption was successfully improving surface property. This membrane combines PAA/PAH and PSS/PAHlayers. The inner layers, PAH/PSS layers, supplied a uniform and higher contact angle porous film. The outmost layer, PAA/PAH layer, provided available surface to react with Pd-complex which is printed by Ink-Jet. Through these treatment processes, we can obtain high performance metal circuits after printing of catalyst and then electroless plating deposition. In addition, we have demonstrated the feasibility of layer by layer polyelectrolyte multilayers for surface treatment, and the catalyst layer patterned by ink-jet method.