In the low earth orbit (LEO), the atomic oxygen(AO) with strong oxidizing ability, large flux and high energy is considered to cause severe hazards to the spacecraft exterior materials. In particular, the interaction of AO with polymer materials results in severe damages of the materials, such as irreversible degradation of optical, electric and mechanical properties, leading to negative influence on the normal operation and shortened served life of the spacecraft. Base on the theoretical basis for study on AO erosion resistant materials in LEO environment, this paper reviewed the preparation methods of inorganic, organic and composite coatings, summarized their advantages and disadvantages and the existing problems, and pointed out the importance to study the mechanisms of coating cracking and interfacial debonding failure. Future research should be focused on self-healing organic or inorganic coatings and the coatings reacted with AO to produce stable oxides or stable surface structure. The polymer matrix and coatings should be taken as a whole to study, and the interfacial effect and failure mechanism between the coatings and matrix should be well studied. In the research field of AO-resistant new materials, using polyimide as an example, the research progresses of phosphorus-containing polyimide, silicon-containing polyimide and zirconium-containing polyimide were introduced, as well as the key problems and technology to be solved in the transformation from basic research to engineering application. It was hoped that this review could provide some research ideas for the development of new advanced protective coatings and new materials.