Dielectric materials demonstrating ultralow permittivity, excellent mechanical property and durability under humid environment are highly demanded for the rapid development of 5G communication systems. Herein, a series of porous fluorinated polyarylene ether nitrile (FPEN) films having ultralow permittivity and excellent mechanical property that can be used under moisture environment are prepared by a delayed phase inversion approach. Due to the introduction of low molar polarity fluorinated substituents and porous structures, the porous FPEN films show ultralow dielectric constant of lower than 1.40 at 1 kHz and hydrophobic surface with the water contact angle higher than 90°. In addition, the porous FPEN films also exhibit an ultralow dielectric constant (<1.42 at 1 kHz) even when placed in a humid environment with a relative humidity of 80% for 72 h. The porous FPEN films demonstrate elongation at break higher than 32%, specific modulus higher than 1260 MPa cm3 g−1, excellent flexibility and foldability. These outstanding properties including the ultralow dielectric properties, hydrophobicity, flexibility, foldability and others facilitate the application of porous FPEN films as 5G communication system dielectrics.