The laminated structure includes a substrate of low dielectric constant material of silicon compound and an electroless copper plating layer laminated thereon with a barrier layer. The barrier layer is interposed between the substrate and the copper layer, and the barrier layer is formed by electroless plating. And the laminated structure is characterized in that the barrier layer is formed on the substrate with a monomolecular layer of organosilane compound and a palladium catalyst which are interposed between the substrate and the barrier layer, the palladium catalyst modifies the terminal, adjacent to the barrier layer, of the monomolecular layer, and the barrier layer includes an electroless NiB plating layer which is disposed on the substrate side, and a electroless CoWP plating layer. The present invention makes it possible to coat the low dielectric constant material of silicon compound in a simple all-wet process with a firmly adhering barrier layer and an electroless copper plating layer as the wiring layer. the advantage of requiring. Thus, the laminated structure formed in this way includes a substrate of low dielectric constant material of silicon compound, a barrier layer, and a copper layer as the wiring layer formed by electroless plating, which firmly adhere to one another. In addition, the laminated structure is suitable for the copper wiring in a ULSI, particularly the one which is to be formed in a narrower trench than conventional one.