The delicate engineering of monovalent cations in perovskite material has led to continuous performance breakthroughs and stability improvement for the perovskite light‐emitting diodes (PeLEDs). However, the exact role of A‐site cations on the electroluminescence (EL) performance and degradation mechanism of PeLEDs has not been systematically answered yet. Herein, it is demonstrated that the most commonly used methylammonium cation (MA+) has an adverse effect on the electrochemical reaction at the interface between perovskite and metal‐oxide layer, leading to deteriorated EL performance as compared to that of the formamidinium cation (FA+)‐based perovskite. It reveals that the accelerated deprotonation process of MA+ under an electric field will aggravate the reaction between iodide and metal ion in oxide layer. The further substitution of a small portion of FA+ with inorganic cesium cation (Cs+) results in much enhanced crystallinity and enlarged crystal size, leading to an optimized peak external quantum efficiency of 21.3%. The ion migration process in the PeLEDs can be significantly suppressed with Cs+ incorporation, leading to a smaller roll‐off under large current density and an elongated half‐lifetime of 190.1 h under a current density of 20 mA cm‐2, representing one of the most stable PeLEDs based on 3D perovskite layer.

Although the electroluminescent performances of perovskite light‐emitting diodes (PeLEDs) are continuously improved through defect management strategies, the complicated design of passivation ligands brings great challenges to the rational defect‐annihilation process. Herein, considering the bonding strength with uncoordinated Pb2+, the methoxy group with strong electron donating ability is introduced to commonly used phenethylammonium ligand as an efficient additive, namely 4‐methoxy‐phenethylammonium iodide (4‐MeO‐PEAI), to facilitate passivation process in perovskite light‐emitting materials. It is demonstrated that the 4‐MeO‐PEAI agent substantially increases the crystal orientation, enlarges the crystalline grain size, and mitigates the deep‐level trap centers through strong bonding between the methoxy group with unpaired Pb2+ ions. The external quantum efficiencyvalue of the PeLEDs with optimized passivation reaches a maximum of 21.6%, with an emission peak of 790 nm. In addition, a nearly threefold increase of the operational half‐lifetime T50 of the 4‐MeO‐PEAI‐mediated devices is observed as compared to the reference sample. Further theoretical calculation results suggest that the adhesion of the ligands on perovskite surface via vacancies leads to an increased dissociation barrier of perovskite; thus, ameliorating the degradation of the PeLEDs under electric field. The findings provide an effective design strategy of the passivation agents to produce high‐performance perovskite‐based optoelectronics devices.