Bonded lubricating coatings for spacecraft are subject to the combined effect of the low-earth orbit environment, ground environment and mechanical wear, making it difficult to meet long-life and high-reliability requirements. In this study, Polydimethylsiloxane (PDMS)-modified polyamide-imide (PAI) /molybdenum disulfide (MoS2) coatings were prepared using a self-stratifying strategy. The structural and tribological performance changes of coatings after atomic oxygen (AO) irradiation were investigated. The results showed that the PDMS segments improved the AO erosion resistance due to the inorganic layer produced on the surface of coating. The structural integrity of the binder and lubricant decreased the effect of AO erosion on the tribological performance of lubricating coatings. The PDMS-PAI/MoS2 coating have application prospects in the field of lubricating coating for spacecraft.