The lagging development of deep‐blue perovskite light‐emitting diodes (PeLEDs) heavily impedes their practical applications in full‐color display due to the absence of spectrally stable emitters and the mismatch of carrier injection capacity. Herein, we report highly efficient deep‐blue PeLEDs through a new chemical strategy that addresses the dilemma for simultaneously constant electroluminescence (EL) spectra and high‐purify phase in reduced‐dimensional perovskites. The success lies in the control of adsorption‐energy differences between phenylbutylamine (PBA) and ethylamine (EA) interacting with perovskites, which facilitates narrow n‐value distribution. This approach leads to an increased exciton binding energy and enhanced surface potential, hence improving radiative recombination. As a result, an external quantum efficiency of 4.62 % is achieved in PeLEDs with a stable EL peak at 457 nm, demonstrating the best reported result for deep‐blue PeLEDs so far. [ABSTRACT FROM AUTHOR]