The thermal shock of subsurface material with shear instability and severe plastic flow during scuffing was investigated. The scuffing damage of M50 steel was tested using a high-speed rolling–sliding contact test rig, and the transient temperature during scuffing was calculated using the Fourier transform method considering the effects of both frictional heat and plastic work. The results show that a thermal shock with a rapid rise and subsequent rapid decrease in the contact temperature is generated in the subsurface layers. The frictional power intensity generates a high temperature rise, leading to the austenitization of the subsurface material. Consequently, the plastic flow is generated in the subsurface layer under the high shear stress, and the resulting plastic strain energy generates a further temperature increase. Subsequently, a rapid decrease in the contact temperature quenches the material, resulting in clear shear slip bands and retained austenite in the subsurface layers of the M50 steel.