Membranes with low dielectric constant and high moisture resistance are the key material for miniaturized and integrated communication equipment as an interlayer dielectric layer. Here, a series of cross-linked PI aerogel membranes were prepared by co-polymerization and scraping coating technology. The introduction of the fluorinated blocks and benzimidazole ring structures can consequently garner novel PI aerogel membranes with fascinating dielectric properties and outstanding moisture resistance. The dielectric constants of the sample membranes are as low as 1.33 at 1 KHz and 1.32 at 1 MHz with dielectric loss as low as 0.0079 at 1 KHz and 0.0035 at 1 MHz. The water contact angle can reach 107.35° with a surface roughness value of 30.428 nm. Moreover, the PI aerogel membranes have high specific surface area and excellent thermal and mechanical properties. The thermal conductivity as low as 35.4 mW m−1 K−1 at room temperature indicates excellent thermal insulation performance. PIAM-2 is suitable as an interlayer dielectric layer for electronic components under harsh environment. In addition, the influence of surface roughness on surface wettability was also elaborated on which can provide a feasible method for the preparation of low dielectric materials with moisture resistance.