Polymers, as substrate of composite material on the surface of spacecraft, have such advantages as light mass and high strength. Atomic oxygen (AO) is one of the highest content particles of low earth orbit, and high-energy high-flux AO bombardment causes the polymers’ surface erosion and mass loss at different degree, resulting in polymers degradation. Thus, AO is one of major threats in space environment that reduces reliability of space devices and shortens their working life span. This review summarized current global protection technologies from AO in recent years. Among them, surface chemical modification method with advantages of body-modification and protection coating, providing organic/inorganic composite with modified layer through comprehensive protection performance. This review discussed the method to explore the AO protection reaction mechanism by computational simulation. Computational simulation combined with experiments may reveal nature of the protection, facilitate future researches on AO protection, and provide guidance for fabrication surface polymer materials used in domestic parts of the aerospace craft, especially the large-scale flexible space solar cell array