Polyimide, which is widely used to insulate power equipment operating in a vacuum environment, is prone to insulation failure due to surface flashover. Using POSS to modify it is an effective solution. This paper focuses on the study of DC surface flashover characteristics in vacuum of POSS/polyimide composite film, by introducing 1%, 3%, 5% equivalent mole content of POSS into polyimide, and conducting a surface flashover characteristics test in vacuum together with pure polyimide. The physical and chemical properties of the composite films were tested utilizing Fourier transform infrared spectroscopy and ultraviolet–visible spectroscopy. Combined with resistivity, SEM, and other test techniques, the influence mechanism of POSS molecular modification on DC surface flashover characteristics of polyimide films in vacuum was initially revealed. The results showed that after the introduction of POSS, the overall functional group structure of polyimide remained unchanged, the intermolecular charge transfer complexation was inhibited, and the transmittance of the film increased. The thermal conductivity and thermogravimetric temperature of the film are improved to a certain extent, and the mechanical properties are slightly decreased. With the increase of the introduced POSS content, the dielectric strength of the composite film is also enhanced. The surface flashover voltage of the composite film with a POSS content of 5% is 17.5 kV in vacuum, which is 30.5% higher than that of the pure film. Further analysis shows that the introduction of POSS will reduce the resistivity of the composite film, accelerate the dissipation of surface charges, and increase the flashover voltage. In addition, POSS forms a uniformly distributed Si-O-Si cage-like structure through molecular modification. When the surface of the film is damaged, SiOx inorganic flocculent particles are generated, which can not only scatter electrons, but also shallow the depth of trap energy level and accelerate the dissipation rate of surface charge, thus increasing the flashover voltage.