Surface structures of the acrylate resin substrates with and without plasma exposure were analyzed by SEM, XPS, and static SIMS in order to examine the influence by plasma exposure prior to sputtered film deposition. In general, both the morphology and composition of a resin surface are changed by plasma exposure. However, it was found that the difference in the surface roughness was hardly discernible at the initial stage of the exposure. On the other hand, surface chemical structures such as functional groups are markedly modified. Furthermore, analysis of XPS valence band spectrum based on the molecular orbital calculation has been successfully applied to distinguish the position of cleaved band in the molecule. The results obtained from XPS and static SIMS analyses are described in detail.