The photodegradation of an amine-cured epoxy coating after exposure to accelerated UV-340 and LTV-313 irradiation was investigated with an atomic-level technique, positron annihilation spectroscopy (PAS), which detected and characterized the free volumes and defects as a function of the depth. Significant changes in the subnanometer defect parameters S and W were observed as a function of the exposure time near the surface. This was interpreted as due to a loss of the free volume and hole fraction resulting from photodegradation. A dead layer near the surface, resulting from UV irradiation from the surface up to a thickness of 0.4 mum, at which there was nearly no positronium formation, was observed. Correlations between physical defects from PAS in terms of the free volumes and chemical defects from electron spin resonance spectroscopy in terms of free radicals and chemical structural changes measured by ultraviolet-visible and Fourier transform infrared spectroscopy were established. A high sensitivity of PAS for detecting the early stage of degradation, on the order of hours for UV-313 and on the order of days for UV-340 irradiation, was observed. (C) 2004 Wiley Periodicals, Inc.