<p>Perovskite solar cells (PSCs) exhibit substantially improved performance and stability; however, maintaining high power conversion efficiency (PCE) and stability while up-scaling cell areas remains challenging. Furthermore, perovskite nucleation and growth are highly sensitive to processing methods, increasing the complexity of large-scale production. To address these challenges, we establish a temperature-controlled vacuum quenching method combined with in situ photoluminescence spectrometry to fabricate perovskite films under monitoring. We systematically study the commonly used quenching nucleation processes and reveal the impact of the pumping speed, solvent system and additives on the vacuum quenching process. We manage to modulate the perovskite nucleation process by lowering the temperature during the vacuum quenching process, thereby broadening the time window for post-processing treatments to obtain high-quality large-area perovskite films. The resultant 1.55 eV mini-module achieves a PCE of 22.69% with an aperture area of 11.7 cm² (and a certified aperture-area PCE of 21.60%), whereas the corresponding PSC maintained &gt;93% of its initial efficiency after continuously operating at 45 °C for 3,500 h under 1 sun illumination. This approach enables high-quality, uniform and large-area perovskite films on rigid, flexible and curved substrates, demonstrating the feasibility of our strategy for improving the scalability of renewable PSC technology.</p>