Ultrafast Programming of Large Curvature Based on Selenium‐Sulfur Dynamic Metathesis

The construction and integration of curvature govern the structure and function of materials based on 2D sheets, yet achieving ultrafast and scalable curvature programming remains a major challenge. We rapidly generate large stress mismatches by combining an ultrafast stress‐relaxing diselenide‐containing polyurethane with an ultraslow stress‐relaxing disulfide‐containing polyurethane. Coupled with modular components and compression, this mismatch enables localized, directional loading of high stress with excellent scalability. Using this strategy, 2D polymer sheets achieve 180° bending within 10 s of UV irradiation, yielding a curvature‐programming rate 15‐fold faster than state‐of‐the‐art methods. Furthermore, origami modules, which display a 37‐fold enhancement in compressive performance, can be obtained through mass production and assembled into complex 3D architectures. This rapid, high‐curvature programming approach offers efficiency, mechanical robustness, and scalability, advancing the practical deployment of origami‐based metamaterials.