Auxetic architectures with a negative Poisson’s ratio have attracted increasing attention due to their intriguing physical properties, numerous promising applications and recent advancements in manufacturing techniques. However, fabrication of three-dimensional (3D) polymeric auxetic architectures with tailored hierarchically porous structure and desired physical/mechanical properties remains challenging. Herein, 3D nanofibrous Kevlar aerogel architectures with porosity at multi-scales have been designed and fabricated through a new additive manufacturing strategy, i.e., integration of direct ink writing and freeze-casting with non-toxic solvent-based inks following special drying techniques. The highly porous 3D nanofibrous Kevlar aerogel architectures achieve excellent mechanical properties with ultralow density (down to 11.9 mg·cm-3) and large specific surface area (up to 350 m2·g-1). The Poisson’s ratio is tunable in a wide range, spanning from −0.8 to 0.4, by adjusting the spatial arrangement of the struts in geometries. Finally, these nanofibrous Kevlar aerogel architectures have been further functionalized into hydrophobic, luminescent and thermal-responsive architectures by using fluorocarbon resin, functional dyes and organic phase-change materials respectively. The multi-functionalizable auxetic aerogel architectures demonstrate potentials for a broad range of applications
