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• MXene/AgNWs aerogels with interpenetrating double-network structure were fabricated. • The porous structure contributes to higher attenuation of electromagnetic waves. • 3D network provides channel for electron and phonon transmission in epoxy composites. • The composites possess remarkable EMI SE and thermal conductivity. The novel multifunctional materials with anti-electromagnetic interference (EMI) and effective thermal management are ideal for modern electronic industry. Generally, the EMI shielding effectiveness (SE) and thermal conductivity (TC) of materials can be effectively enhanced by compounding with high electrically and thermally conductive fillers. However, it seems that the high-performance cannot be compensated without sacrificing the high fillers loading. Herein, from one-dimensional silver nanowires (AgNWs) and two-dimensional MXene, three-dimensional MXene/AgNWs aerogels were designed as electric and heat transferring skeletons for epoxy nanocomposites by directional-freezing and freeze-drying methods. The resultant MXene/AgNWs/Epoxy nanocomposites with a low MXene/AgNWs content of 8.2 wt% combine a high electrical conductivity of 1532 S/m, and an exceptional EMI SE value of 94.1 dB with 3 mm thickness at the X-band frequency, as well as an improved TC of 2.34 W/m·K. The fabricated MXene/AgNWs/Epoxy nanocomposites possess excellent comprehensive properties enable valuable applications in electronic devices for EMI shielding and thermal management. [ABSTRACT FROM AUTHOR]