LAUSR

Solution‐processed metal halide perovskites (MHPs) have attracted much attention for applications in light‐emitting diodes (LEDs) due to their wide color gamut, high color purity, tunable emission wavelength, balanced electron/hole transportation, etc. Although MHPs are very tolerant to defects, the defects in solution‐processed perovskite LEDs (PeLEDs) still cause severe nonradiative recombination and device instability. Here, molecular design of additives for dual passivation of both lead and halide defects in perovskites is reported. A bi‐functional additive, 4‐fluorophenylmethylammonium‐trifluoroacetate (FPMATFA), is synthesized by using a simple solution process. The TFA anions and FPMA cations can bond with undercoordinated lead and halide ions, respectively, resulting in dual passivation of both lead and halide defects. In addition, the bulky FPMA group can constrain the grain growth of 3D perovskite, enhancing electron–hole capture rates and radiative recombination rates. As a result, high‐performance PeLEDs with a peak external quantum efficiency reaching 20.9% and emission wavelength at 694 nm are achieved using formamidinium‐cesium lead iodide‐bromide (FA0.33Cs0.67Pb(I0.7Br0.3)3). Furthermore, the operational lifetime of PeLEDs is also greatly improved due to the low trap density in the perovskite film.