Developing functional additive resistant to space atomic oxygen (AO) irradiation through simple molecular design and chemical synthesis to enhance the lubricating performance of multialkylated cyclopentanes (MACs) oil is a significant challenge. Herein, sulfur-containing polyhedral oligomere silsesquioxane (POSS) were synthesize via a click-chemistry reaction of octavinyl polyhedral oligomeric with alkyl sulfide. The reduce-friction (RF), anti-wear (AW) properties and anti-AO irradiation of POSS-S-R as MACs base oil additives in atmospheric and simulated space environments were systematically investigated for the first time. Results demonstrate that POSS-S-R not only possesses outstanding anti-AO irradiation capacity but also effectively improves the RF and AW of MACs in atmospheric or simulated space surroundings. This improvement is due to the excellent anti-AO irradiation properties of the POSS structure itself and the high load-carrying ability of silicon-containing and sulfur-containing compounds generated by tribo-chemical reactions, which effectively separates the direct contact of the friction interface. We believe that this synthesized POSS-S-R is a promising additive for space lubricants.