With a certified efficiency as high as 25.2%, perovskite has taken the crown as the highest efficiency thin film solar cell material. Unfortunately, serious instability issues must be resolved before perovskite solar cells (PSCs) are commercialized. Aided by theoretical calculation, an appropriate multifunctional molecule, 2,2‐difluoropropanediamide (DFPDA), is selected to ameliorate all the instability issues. Specifically, the carbonyl groups in DFPDA form chemical bonds with Pb2+ and passivate under‐coordinated Pb2+ defects. Consequently, the perovskite crystallization rate is reduced and high‐quality films are produced with fewer defects. The amino groups not only bind with iodide to suppress ion migration but also increase the electron density on the carbonyl groups to further enhance their passivation effect. Furthermore, the fluorine groups in DFPDA form both an effective barrier on the perovskite to improve its moisture stability and a bridge between the perovskite and HTL for effective charge transport. In addition, they show an effective doping effect in the HTL to improve its carrier mobility. With the help of the combined effects of these groups in DFPDA, the PSCs with DFPDA additive achieve a champion efficiency of 22.21% and a substantially improved stability against moisture, heat, and light. Aided by theoretical calculations, a multifunctional 2,2‐difluoropropanediamide (DFPDA) molecule that bears carbonyl, amino, and fluorine groups is first introduced into the perovskite precursor, serving as a crystal growth mitigator, grain boundaries passivator, and surface protection material. With the help of the combined effects of multifunctional groups in DFPDA, the perovskite cells deliver an efficiency of 22.21% and improved stability.