A process is provided for metallizing a surface of a substrate with electrolytically plated copper metallization, the process comprising electrolytically depositing copper over the electrically conductive polymer by immersing the substrate in an electrolytic composition and applying an external source of electrons, wherein the electrolytic composition comprises a source of copper ions and has a pH between about 0.5 and about 3.5. In another aspect, a process is provided for metallizing a surface of a dielectric substrate with electrolytically plated copper metallization, the process comprising immersing the substrate into a catalyst composition comprising a precursor for forming an electrically conductive polymer on the surface of the dielectric substrate and a source of Mn(II) ions in an amount sufficient to provide an initial concentration of Mn(II) ions of at least about 0.1 g/L to form an electrically conductive polymer on the surface of the dielectric substrate, and electrolytically depositing copper over said electrically conductive polymer.