Simultaneous improvement in dielectric, water resistance and mechanical properties of polyimide (PI) films is critical for their practical use, but difficult to achieve. Herein, a sandwich-type porous GO/PI film with excellent comprehensive properties was obtained through integrating a GO-containing complex, fluorine-containing porous structure and sandwich-type distribution of porous structure by a simple, low-cost and green breath figure method. With the addition of only a small amount of GO-containing complex, a low dielectric constant of 2.21, water absorption of 0.51%, increment in dielectric constant after moisture treatment of 1.60% and high tensile strength of 113.1?MPa, tensile modulus of 1.70?GPa, with 35.39%, 79.42%, 81.81% of reduction and 17.22%, 21.43% of increase compared to PI film were shown, respectively. Moreover, these properties could be adjusted through regulating the component and porous structure by changing the parameters of breath figure method. These outstanding properties make the film a promising candidate for high-performance low-dielectric materials.