Highly Robust Conductive Organo‐Hydrogels with Powerful Sensing Capabilities Under Large Mechanical Stress

Abstract The low mechanical strength of conductive hydrogels (<1 MPa) has been a significant hurdle in their practical application, as they are prone to fracturing under complex conditions, limiting their effectiveness. Here, this work fabricates a strong and tough conductive hierarchical poly(vinyl alcohol) (PEDOT:PSS/PVA) organo‐hydrogel (PPS organo‐hydrogel) via a facile combining strategy of self‐assembly and stretch training. With PVA/PEDOT:PSS microlayers and aligned PVA/PEDOT:PSS nanofibers, PVA and PEDOT:PSS nanocrystalline domains, and semi‐interpenetrating polymer networks, PPS organo‐hydrogels display outstanding mechanical performances (strength: 54.8 MPa, toughness: 153.97 MJ m⁻³). Additionally, PPS organo‐hydrogels also exhibit powerful sensing capabilities (gauge factor (GF): 983) due to the aligned hierarchical structures and organic liquid phase of DMSO. Notably, with the synergy of such mechanical and sensing properties, organo‐hydrogels can even detect objects as light as 1 gram, despite bearing a tensile strength of ≈23 MPa. By incorporating these materials into human‐machine interfaces, such as controlling artificial arms for grabbing objects and monitoring sport behaviors in soccer training, this work has unlocked a new realm of possibilities for these high‐performance hierarchical organo‐hydrogels. This approach to designing hierarchical structures has the potential to lead to even more high‐performance hydrogels in the future.