In this article, the surface-layer structure evolution of carbon fibers along the cross-section γ-irradiated in epoxy chloropropane has been estimated by X-ray photoelectron spectroscopy combined with in situ argon-ion sputtering that is different from argon-ion cleaning. In argon-ion (Arion) sputtering, the detection and sputtering were alternately in situ carried out. The penetration depth of irradiation medium on the surface of carbon fibers was accurately verified (13 nm) according to the absence of chlorine element and the change of O/C atomic ratio on γ-irradiated carbon fiber surface. Such characterization technology has opened up a meaningful method to analyze the heterogeneous structure of materials. POLYM. COM-POS., 40:E832-E834, 2019.