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The power conversion efficiency of organic–inorganic hybrid perovskite solar cells has increased rapidly, but the device stability remains a big challenge. Previous studies show the grain boundary (GB) can facilitate ion migration and initiate device degradation. Herein, methimazole (MMI) is employed for the first time to construct a surface “patch” by in situ converting residual PbI₂ at GBs. The resultant MMI–PbI₂ complex can effectively suppress ion migration and inhibit diffusion of the metal electrodes. The origin of the surface “patch” effect and their working mechanisms are investigated experimentally and theoretically at the microscopic level. It hence demonstrates a simple and effective method to prolong the device stability in the context of GB engineering, which could be extensively applied to perovskite‐based optoelectronics.