An epoxy coating applied to the concrete surface of a containment building deteriorates in hazardous environments such as those containing radiation, heat, and moisture. Unlike metals, the epoxy coating on a concrete liner absorbs and discharges moisture during the degradations process, so it has a different density and volume during service. In this study, acoustic impedance was adopted for characterizing the degradation of a glass-reinforced epoxy coating using the acoustic reflection coefficient (reflectance) on a rough epoxy coating. For estimating the acoustic reflectance on a wavy epoxy coating surface, a probabilistic model was developed to represent the multiple irregular reflections of the acoustic wave from the wavy surface on the basis of the simulated annealing technique. A number of epoxy-coated concrete specimens were prepared and exposed to accelerated aging conditions to induce an artificial aging degradation in them. The acoustic impedance of the degraded epoxy coating was estimated successfully by minimizing the error between a waveform calculated from the mathematical model and a waveform measured from the surface of the rough coating.