Architectural Tuning of Bouligand Electrospun Laminates Enables Coupled Mechanical Robustness and Electromechanical Sensing

Nature provides design principles that enable multifunctional materials to combine mechanical resilience with specialized functionality. Translating hierarchical biological architectures into compliant synthetic systems capable of integrated sensing and human‐machine interfacing, however, remains largely unexplored. Here, we analyze the helicoidal Bouligand organization of the blue crab (Callinectes sapidus) exoskeleton and translate this principle into biodegradable electrospun poly(L‐lactide‐co‐ε‐caprolactone) (PLCL) laminates with embedded carbon nanotube (CNT) sensing layers. By varying the angular rotation between fiber layers while maintaining identical composition, we isolate the influence of laminate architecture on mechanical and electromechanical performance. A 20° interlayer rotation provides the most balanced mechanical response, increasing Young's modulus more than threefold and tensile strength by almost 40% relative to randomly stacked laminates. Despite being around 100 µm thick, the laminates withstand out‐of‐plane deformations exceeding 55 to 73 times their thickness before failure, while the embedded CNT network enables real‐time detection of structural damage. After textile integration, laminates function as wearable sensors for touch, strain, temperature, and weight, with laminate architecture producing over an order of magnitude variation in electrical output. As a proof‐of‐concept human‐machine interface, the laminates enable real‐time signal visualization and synchronized robotic hand actuation, demonstrating a scalable strategy for smart materials and bioinspired structural electronics.