This study firstly reports a series of novel functional polyhedral oligomeric silsesquioxane-based ionic liquids (POSS-ILs) with remarkable lubrication performance as well as resistance to space atomic oxygen (AO) irradiation. The enhancement in both anti-irradiation properties and the lubrication performance can be attributed to the synergistic effect produced by POSS group along with the tribochemical reactions. The approximate cubeoctameric POSS framework as a significant contributor converts the original sliding friction into a rolling mode. The key benefit of POSS-ILs derives from the active elements N and P present in ILs and corresponding tribochemical reaction film formed. These ILs are bound to have substantial applicability in the aviation lubrication field.