This study presents the preparation of a flexible nanofiber composite membrane with a twill surface structure, inspired by the Chinese Knotting weave. The membrane, composed of poly(vinyl alcohol-co-ethylene) (Pva-co-PE) nanofibers and MXene/silver nanowires (MXene/AgNW), exhibited excellent electromagnetic interference (EMI) shielding efficiency (SE) of 103.9 dB with only 7.4 wt% MXene/AgNW content. The twill surface structure improved EMI SE by 38.5%, enhancing the pre-interference of incident EM waves and increasing internal reflection and loss. The membrane demonstrated superior thermal management, hydrophobicity, non-flammability, and performance stability, maintaining 97.3% EMI SE at 140 °C. The twill structure, combined with the porous internal structure and matching of the absorbing media, synergistically enhanced EMI SE. This study provides a new approach for preparing thin, flexible, and highly efficient EMI shielding materials.This study presents the preparation of a flexible nanofiber composite membrane with a twill surface structure, inspired by the Chinese Knotting weave. The membrane, composed of poly(vinyl alcohol-co-ethylene) (Pva-co-PE) nanofibers and MXene/silver nanowires (MXene/AgNW), exhibited excellent electromagnetic interference (EMI) shielding efficiency (SE) of 103.9 dB with only 7.4 wt% MXene/AgNW content. The twill surface structure improved EMI SE by 38.5%, enhancing the pre-interference of incident EM waves and increasing internal reflection and loss. The membrane demonstrated superior thermal management, hydrophobicity, non-flammability, and performance stability, maintaining 97.3% EMI SE at 140 °C. The twill structure, combined with the porous internal structure and matching of the absorbing media, synergistically enhanced EMI SE. This study provides a new approach for preparing thin, flexible, and highly efficient EMI shielding materials.