Chemical bonding at polymer surface is an important factor because it relates to the fundamental properties of polymers such as wettability and adhesion specially in industrial applications. In this study, NEXAFS (Near Edge X-ray Absorption Fine Structure) spectroscopy using synchrotron radiation was applied to the characterization of polymer surfaces. The spectrum provided a good deal of information related to chemical bond that is difficult to obtain by X-ray photoelectron spectroscopy. The usefulness of NEXAFS spectroscopy as a method of polymer surfaces characterization is demonstrated.