Carborane-containing aromatic polyimide (CPI) films with ultrahigh thermo-oxidative stability at 700 °C have been prepared by casting poly(amic acid) (PAA) resin solution on a glass surface, followed by thermal imidization at elevated temperatures. The PAA solution was prepared by copolymerization of an aromatic dianhydride and an aromatic diamine mixture, including carborane-containing aromatic diamine in an aprotic solvent. The CPI films showed excellent thermo-oxidative stability at 700 °C due to the multilayered protection layers formed on the film surface by thermal conversion of the carborane group into boron oxides. The boron oxide layer enhanced the degradation activation energy and suppressed the direct contact of inner polymer materials with oxygen molecules in a high-temperature environment, acting as a “self-healing” skin layer on the polyimide materials. The CPI-50 film was still flexible and maintained 50% retention of mechanical strength even after thermo-oxidative aging at 700 °C/5 min. The mechanism of thermo-oxidative degradation was proposed.