Ion migration‐induced intrinsic instability and large‐area fabrication pose a tough challenge for the commercial deployment of perovskite photovoltaics. Herein, we develop an interface heterojunction and metal electrode stabilization strategy by suppressing ion migration via managing lead‐based imperfections. After screening a series of cations and nonhalide anions, the ideal organic salt molecule dimethylammonium trifluoroacetate (DMATFA) consisting of dimethylammonium (DMA+) cation and trifluoroacetate (TFA−) anion is selected to manipulate the surface of perovskite films. DMA+ enables the conversion of active excess and/or unreacted PbI2 into stable new phase DMAPbI3, inhibiting photodecomposition of PbI2 and ion migration. Meanwhile, TFA− can suppress iodide ion migration through passivating undercoordinated Pb2+ and/or iodide vacancies. DMA+ and TFA− synergistically stabilize the heterojunction interface and silver electrode. The DMATFA‐treated inverted perovskite solar cells and modules achieve a maximum efficiency of 25.03% (certified 24.65%, 0.1 cm2) and 20.58% (63.74 cm2), respectively, which is the record efficiency ever reported for the devices based on vacuum flash evaporation technology. The DMATFA modification results in outstanding operational stability, as evidenced by maintaining 91% of its original efficiency after 1520 h of maximum power point (MPP) continuous tracking.This article is protected by copyright. All rights reserved