Image credit: WileyThe 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.