Since thermosetting resins have excellent resistance to chemicals, fiber reinforced plastics composed of such resins and reinforcement fibers are widely used as construction materials for equipment in chemical plants. Such equipment is usually used for several decades under severe corrosive conditions so that failure due to degradation may result. One of the degradation behaviors in thermosetting resins under chemical solutions is “corrosion-layer-forming” degradation. In this type of degradation, surface resins in contact with a solution corrode, and some of them remain as a corrosion layer on the pristine part. It is difficult to precisely measure the thickness of the pristine part of such degradation type materials by conventional pulse-echo ultrasonic testing, because the sound velocity depends on the degree of corrosion of the polymeric material. In addition, the ultrasonic reflection interface between the pristine part and the corrosion layer is obscure. Thus, we propose a pitch-catch method using a pair of normal and angle probes to measure four parameters: the thicknesses of the pristine part and the corrosion layer, and their respective sound velocities. The validity of the proposed method was confirmed by measuring a two-layer sample and a sample including corroded parts. The results demonstrate that the pitch-catch method can successfully measure the four parameters and evaluate the residual thickness of the pristine part in the corrosion-layer-forming sample.