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Abstract Perovskite light‐emitting diodes (PeLEDs) are advancing because of their superior external quantum efficiencies (EQEs) and color purity. Still, additional work is needed for blue PeLEDs to achieve the same benchmarks as the other visible colors. This study demonstrates an extremely efficient blue PeLED with a 488 nm peak emission, a maximum luminance of 8600 cd m⁻², and a maximum EQE of 12.2% by incorporating the double‐sided ethane‐1,2‐diammonium bromide (EDBr₂) ligand salt along with the long‐chain ligand methylphenylammonium chloride (MeCl). The EDBr₂successfully improves the interaction between 2D perovskite layers by reducing the weak van der Waals interaction and creating a Dion–Jacobson (DJ) structure. Whereas the pristine sample (without EDBr₂) is inhibited by small stacking number (n) 2D phases with nonradiative recombination regions that diminish the PeLED performance, adding EDBr₂successfully enables better energy transfer from smallnphases to largernphases. As evidenced by photoluminescence (PL), scanning electron microscopy (SEM), and atomic force microscopy (AFM) characterization, EDBr₂improves the morphology by reduction of pinholes and passivation of defects, subsequently improving the efficiencies and operational lifetimes of quasi‐2D blue PeLEDs.