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The oxidation and erosion of atomic oxygen are considered to be the most dangerous environmental factors for materials exposed to the aerospace environment. In order to investigate the effect of atomic oxygen on the lubricating film and improve the tribological properties, MoS2–WS2 composite film was prepared by the sputtering technique. The film structure and mechanical behavior were characterized and their vacuum tribological properties were evaluated by a friction tester. The composite film possessed better atomic oxygen (AO) resistance than pure film because of the dense structure. The tribological performance of composite film was different under the conditions after AO-irradiation and sliding and during AO-irradiation. After AO-irradiation, the tribological properties of composite film were similar to those before AO-irradiation. However, high friction noise, wear rate, and reduced wear duration were observed for the composite film under the AO-irradiation/friction process because of the continuous damage of the lubricating film due to the AO-irradiation. The addition of 16 at.% WS2 to the MoS2-based film changed the composite film structure and improved the oxidation resistance of the film, making the composite film exhibit better tribological performance than pure MoS2. [ABSTRACT FROM AUTHOR]