Vapor‐Phase Grain‐Boundary Anchoring Enables Molecular Toughening and Record Bending Endurance in Pilot‐Scale Roll‐to‐Roll‐Printed Flexible Perovskite Modules

Flexible lead‐halide perovskite solar modules with carbon electrodes (C‐fPSMs) are promising for printed photovoltaics due to their low cost and compatibility with roll‐to‐roll (R2R) fabrication. However, the mechanical fragility of microcrystalline perovskite films, arising from their high grain‐boundary density, limits their practical application. Here, we report a vapor‐phase grain‐boundary anchoring strategy via thiol vapor annealing to molecularly toughen printed perovskite layers. Thiol molecules interact with intermediate species and preferentially anchor at surfaces and grain boundaries, reprogramming crystallization across the film. This chemomechanical conditioning promotes grain growth, reduces trap density, and transforms the deformation behavior from brittle fracture to ductile strain accommodation, as evidenced by reduced Young's modulus, increased yield strain, and significantly enhanced fracture toughness. As a result, treated devices retain 93% of their initial performance after 25 000 bending cycles, representing a new benchmark for flexible perovskite cells. In addition, improved film uniformity and interfacial contact enable power conversion efficiencies of 15.7% for R2R‐printed cells and 12.1% for modules (20.25 cm 2 ), with scalability demonstrated up to 900 cm 2 (17.26%). This work provides a scalable strategy to simultaneously enhance mechanical robustness and photovoltaic performance.