Scalable fabrication of perovskite films with homogeneous structure remains a critical challenge in bridging power conversion efficiency gap between solar modules and laboratory-scale cells. To address this, we propose a slot-die coating strategy with pyrrodiazole additives in the perovskite precursor solution to simultaneously immobilize lead iodide and formamidinium iodide. This approach enhances wet film stability by suppressing colloidal aggregation, retards the crystal growth process, and ensures a consistent growth rate across the films. These effects promote the formation of large, monolithic grains, enabling large-area perovskite films with homogeneous structure, excellent uniformity, and low defect density under ambient conditions. Using this strategy, we achieved 10 cm × 10 cm inverted perovskite solar modules with a certified efficiency of 20.3%, along with good working stability and excellent application demonstration, showcasing its great potential for industrialization. Yuan et al. report pyrrodiazole additives for simultaneous immobilizing of lead iodide and formamidinium iodide during slot-die coating perovskite films in air, ensuring consistent growth rate for upper and lower layers of the film, leading to certified efficiency of 20.3% for 10 cm × 10 cm solar modules.