Nature builds biological materials from limited ingredients, however, with unparalleled mechanical performances compared to artificial materials, by harnessing inherent structures across multi‐length‐scales. In contrast, synthetic material design overwhelmingly focuses on developing new compounds, and fails to reproduce the mechanical properties of natural counterparts, such as fatigue resistance. Here, a simple yet general strategy to engineer conventional hydrogels with a more than 100‐fold increase in fatigue thresholds is reported. This strategy is proven to be universally applicable to various species of hydrogel materials, including polysaccharides (i.e., alginate, cellulose), proteins (i.e., gelatin), synthetic polymers (i.e., poly(vinyl alcohol)s), as well as corresponding polymer composites. These fatigue‐resistant hydrogels exhibit a record‐high fatigue threshold over most synthetic soft materials, making them low‐cost, high‐performance, and durable alternatives to soft materials used in those circumstances including robotics, artificial muscles, etc.

Materials with circumferentially aligned fibers, such as intervertebral discs and arteries, are abundant in nature but challenging to replicate artificially, despite their mechanical advantages. Although ice-templating can create bioinspired materials, the achievable structures remain limited to simple forms, such as honeycomb, lamellar, and radial structures. Here, we developed a unique ice-templating technique that constructs circumferential fibrous structures in hydrogels through slow freezing. Enhanced with rotary compression annealing, these hydrogels exhibit record-breaking features that cannot concurrently be achieved in conventional ice-templated and top-performing tough hydrogels, including high tensile properties, isotropic fatigue threshold of 2320 joules per square meter, ultracompressibility (8% strain after 500 cycles), and extraordinary burst pressure of 1.6 bar while maintaining 85 weight % water content. These properties enable opportunities in robotics, including hydrogel pneumatic grippers and an untethered bioinspired robotic fish that exhibits high-force actuation and long-term robustness. Our approach enriches the diversity of bioinspired structures in artificial materials, establishing exceptional mechanical properties through cross-length scale structural design.

High-performance flexible sensors capable of direct integration with biological tissues are essential for personalized health monitoring, assistive rehabilitation, and human–machine interaction. However, conventional devices face significant challenges in achieving conformal integration with biological surfaces, along with sufficient biomechanical compatibility and biocompatibility. This research presents an in situ 3D biomanufacturing strategy utilizing Direct Ink Writing (DIW) technology to fabricate functional bioelectronic interfaces directly onto human skin, based on a novel annealing PEDOT:PSS/PVA composite bio-ink. Central to this strategy is the utilization of a novel annealing PEDOT:PSS/PVA composite material, subjected to specialized processing involving freeze-drying and subsequent thermal annealing, which is then formulated into a DIW ink exhibiting excellent printability. Owing to the enhanced network structure resulting from this unique fabrication process, films derived from this composite material exhibit favorable electrical conductivity (ca. 6 S/m in the dry state and 2 S/m when swollen) and excellent mechanical stretchability (maximum strain reaching 170%). The material also demonstrates good adhesion to biological interfaces and high-fidelity printability. Devices fabricated using this material achieved good conformal integration onto a finger joint and demonstrated strain-sensitive, repeatable responses during joint flexion and extension, capable of effectively transducing local strain into real-time electrical resistance signals. This study validates the feasibility of using the DIW biomanufacturing technique with this novel material for the direct on-body fabrication of functional sensors. It offers new material and manufacturing paradigms for developing highly customized and seamlessly integrated bioelectronic devices.