To bridge the technology gap between IC-level and board-level fabrications, a fully additive selective metallization has already been demonstrated in the literature. In this article, the surface characterization of each step involved in the fabrication process is outlined with bulk metallization of the surface. This production technique has used polyurethane as epoxy resin and proprietary grafting chemistry to functionalize the surface with covalent bonds on an FR-4 base substrate. The surface was then metalized using an electroless copper (Cu) bath. This sequential growth of layers on top of each other using an actinic laser beam and palladium (Pd) ions to deposit Cu is analyzed. State-of-the-art material characterization techniques were employed to investigate process mechanism at the interfaces. Density functional theory calculations were performed to validate the experimental evidence of covalent bonding of the layers. This manufacturing approach is capable of adding metallic layers in a selective manner to the printed circuit boards at considerably lower temperatures. A complete analysis of the process using bulk deposition of the materials is illustrated in this work.