The novel fluorine-containing trisilahydrocarbon lubricants with methyl and 3,3,3-trifluoropropyl substituents (named SiFCH) were synthesized. Importantly, as potential aerospace lubricants, their chemical, physical, and tribological properties under simulated atomic oxygen (AO) exposure in space environment were investigated by a laboratory-built simulation multifunctional space tribo-tester system. The results showed that the SiFCH synthetic oils possess good physical properties and favorable tribological performance, which are superior to that of multi-alkylated cyclopentanes (MACs) in terms of frictional reduction and antiwear capacity under vacuum.