A twill surface structure was introduced to a nanofiber composite membrane to enhance its electromagnetic interference (EMI) shielding performance. Inspired by the Chinese Knotting weave structure, a twill surface was created on a composite membrane made of poly(vinyl alcohol-co-ethylene) (Pva-co-PE) nanofibers and twill nylon fabric. The membrane was prepared using a template method, with a Pva-co-PE-MXene/silver nanowire (Pva-co-PE-MXene/AgNW, PMxAg) membrane. When the MXene/AgNW content was 7.4 wt%, the EMI shielding efficiency (SE) of the composite membrane with the twill surface was 103.9 dB, with the surface twill structure improving the EMI by 38.5%. This improvement was attributed to the pre-interference of the oblique twill structure in the direction of the incident EM wave, which enhanced the probability of electromagnetic waves randomly colliding with the MXene nanosheets. Simultaneously, internal reflection and ohmic and resonance losses were enhanced. The PM7.4Ag membrane with the twill structure exhibited an outstanding tensile strength of 22.8 MPa and an EMI SE/t of 3925.2 dB cm⁻¹. The PMxAg nanocomposite membranes also demonstrated excellent thermal management performance, hydrophobicity, non-flammability, and performance stability, with an EMI SE of 97.3% in a high-temperature environment at 140 °C. The successful preparation of surface-twill composite membranes makes it difficult to achieve both a low filler content and a high EMI SE in electromagnetic shielding materials. This strategy provides a new approach for preparing thin membranes with excellent EMI properties. The composite membrane also demonstrated excellent mechanical properties, including high tensile strength, good flexibility, and resistance to compression. The membrane also exhibited excellent thermal management properties, with the ability to rapidly heat and cool, and it was non-flammable and hydrophobic. The composite membrane showed excellent performance stability, with the EMI SE remaining above 97% even after 2000 cycles of bending at high ambient temperatures. The results demonstrated that the twill structure played a critical role in the attenuation process of the EM waves. The composite membrane also showed excellent EMI performance, with a high EMI SE of 78.9 dB, EMI SE/t of 4824.6 dB cm⁻¹, and SSE/t of 20,068.2 dB cm² g⁻¹. The results demonstrated that the twill structure significantly enhanced the EMI performance of the composite membrane. The composite membrane also showed excellent mechanical properties, including high tensile strength, good flexibility, and resistance to compression. The membrane also exhibited excellent thermal management propertiesA twill surface structure was introduced to a nanofiber composite membrane to enhance its electromagnetic interference (EMI) shielding performance. Inspired by the Chinese Knotting weave structure, a twill surface was created on a composite membrane made of poly(vinyl alcohol-co-ethylene) (Pva-co-PE) nanofibers and twill nylon fabric. The membrane was prepared using a template method, with a Pva-co-PE-MXene/silver nanowire (Pva-co-PE-MXene/AgNW, PMxAg) membrane. When the MXene/AgNW content was 7.4 wt%, the EMI shielding efficiency (SE) of the composite membrane with the twill surface was 103.9 dB, with the surface twill structure improving the EMI by 38.5%. This improvement was attributed to the pre-interference of the oblique twill structure in the direction of the incident EM wave, which enhanced the probability of electromagnetic waves randomly colliding with the MXene nanosheets. Simultaneously, internal reflection and ohmic and resonance losses were enhanced. The PM7.4Ag membrane with the twill structure exhibited an outstanding tensile strength of 22.8 MPa and an EMI SE/t of 3925.2 dB cm⁻¹. The PMxAg nanocomposite membranes also demonstrated excellent thermal management performance, hydrophobicity, non-flammability, and performance stability, with an EMI SE of 97.3% in a high-temperature environment at 140 °C. The successful preparation of surface-twill composite membranes makes it difficult to achieve both a low filler content and a high EMI SE in electromagnetic shielding materials. This strategy provides a new approach for preparing thin membranes with excellent EMI properties. The composite membrane also demonstrated excellent mechanical properties, including high tensile strength, good flexibility, and resistance to compression. The membrane also exhibited excellent thermal management properties, with the ability to rapidly heat and cool, and it was non-flammable and hydrophobic. The composite membrane showed excellent performance stability, with the EMI SE remaining above 97% even after 2000 cycles of bending at high ambient temperatures. The results demonstrated that the twill structure played a critical role in the attenuation process of the EM waves. The composite membrane also showed excellent EMI performance, with a high EMI SE of 78.9 dB, EMI SE/t of 4824.6 dB cm⁻¹, and SSE/t of 20,068.2 dB cm² g⁻¹. The results demonstrated that the twill structure significantly enhanced the EMI performance of the composite membrane. The composite membrane also showed excellent mechanical properties, including high tensile strength, good flexibility, and resistance to compression. The membrane also exhibited excellent thermal management properties