Embedding of active devices in a printed circuit board has increasingly been adopted as a future electronic technology due to its promotion of high density, high speed and high performance. One responsible technology is to embedded active device into a dielectric substrate with a build-up process, for example a chipin-substrate (CiS) structure. In this study, desmear treatment was performed before Cu metallization on an FR-4 surface in order to improve interfacial adhesion between electroless-plated Cu and FR-4 substrate in Cu via structures in CiS systems. Surface analyses using atomic force microscopy and x-ray photoemission spectroscopy were systematically performed to understand the fundamental adhesion mechanism; results were correlated with peel strength measured by a 90o peel test. Interfacial bonding mechanism between electrolessplated Cu and FR-4 substrate seems to be dominated by a chemical bonding effect resulting from the selective activation of chemical bonding between carbon and oxygen through a rearrangement of C-C bonding rather than from a mechanical interlocking effect. In fact, desmear wet treatment could result in extensive degradation of FR-4 cohesive strength when compared to dry surface-treated Cu/FR-4 structures.