In order to deal with the more complex electromagnetic radiation environment, there is highly desirable to manufacture a high-performance electromagnetic shielding material with excellent electromagnetic shielding efficiency, flexibility, thermal properties, fatigue resistance, and other qualities. In this paper, we fabricated an ultralight, flexible, and heat-resistant poly-m-phenylene isophthalamide (PMIA)/Ag nanowires(AgNWs)/Ni composite nanofiber film via electrospinning, spray coating, and electroless plating. Compared with different AgNWs spraying contents, the highest electromagnetic shielding effectiveness, about 96 dB with a thickness of ∼150 µm, is generated by spraying 33.333 mg/cm2 AgNWs suspension. Additionally, because of the benefit of the PMIA, this PMIA/AgNW/Ni composite membrane maintains a constant EMI SE value (over 90 dB) after a high-temperature process under 200 °C, which only decreases by 3.33 %. The excellent performance of the material is due to its large porosity and sandwich structure, which can dissipate electromagnetic waves within the material, with only a very small portion of the electromagnetic waves passing through it. Therefore, this material has a potential application for use in diverse harsh settings.