The mechanisms of propellant gas chemical erosion on gun barrel materials are discussed creatively from a microscopic perspective of molecular diffusion and intermolecular interaction. The influence of high-temperature and high-pressure propellant gas atoms on the shallow surface microstructure of the barrel material is theoretically analyzed using the molecular dynamics simulation method, which can be used as a new idea for further study of the gun barrel erosion mechanism. The results show that the diffusion of the propellant gas atoms into the barrel material can be characterized by the significant longitudinal distribution characteristics of propellant gas atoms and the normal stress distribution characteristics in the surface layer of the barrel. Moreover, the diffusion ability of the propellant gas atoms in the surface of the barrel material decreases gradually with the increasing diffusion depth. Under the action of propellant gas atoms, the dislocation structure dominated by face-centered cubic structure (FCC) forms in the shallow surface of the barrel material. The production of initial erosion in the shallow surface of barrel materials can be predicted by the continual growth of the new structure and the stress distribution characteristics of the material. In addition, the temperature variation of the propellant gas contributes significantly to barrel material erosion.