A series of monodisperse polystyrene/polyethylene tapered block copolymers, with known carbon sp(2)/sp(3) ratios, was evaluated by X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS). The principal component of the Cls peak exhibited no useful variation in shape as the sp(2) concentration was varied. The valence band spectra, however, were found to vary in a systematic manner with the sp(2) concentration. This variation was reflected in the X-ray excited C KLL Auger peak, the structure of the Auger peak providing a ready characterization of the carbon sp(2) concentration. The problem of determining the Sp(2)/Sp(3) ratio in hydrogenated amorphous carbon is discussed.