Trifluoromethyl group-containing polyimides not only show extraordinary electrical properties, but they also exhibit excellent long-term thermo-oxidative stability. Among the most thermomechanically stable structural polyimides are those from 6F dianhydride (6FDA) and 6F diamines. The effects of substituting non-fluorine containing monomers such as BTDA, mPDA and 4,4′-DADPS for the hexafluoroisopropylidene monomers on the dielectric, thermo-oxidative, thermal and mechanical properties of the copolymers were studied.